Electrolytes for lithium ion batteries

ABSTRACT

Electrolytes, lithium ion cells and corresponding methods are provided, for extending the cycle life of fast charging lithium ion batteries. The electrolytes are based on fluoroethylene carbonate (FEC) and/or vinylene carbonate (VC) as the cyclic carbonate component, and possibly on ethyl acetate (EA) and/or ethyl methyl carbonate (EMC) as the linear component. Proposed electrolytes extend the cycle life by factors of two or more, as indicated by several complementary measurements.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.15/447,889, filed on Mar. 2, 2017, and a continuation-in-part of U.S.application Ser. No. 15/447,784, filed on Mar. 2, 2017, both claimingthe benefit of U.S. Provisional Application Nos. 62/319,341, filed Apr.7, 2016, 62/337,416, filed May 17, 2016, 62/371,874, filed Aug. 8, 2016,62/401,214, filed Sep. 29, 2016, 62/401,635, filed Sep. 29, 2016,62/421,290, filed Nov. 13, 2016, 62/426,625, filed Nov. 28, 2016,62/427,856, filed Nov. 30, 2016, 62/435,783, filed Dec. 18, 2016 and62/441,458, filed Jan. 2, 2017, this application further claims thebenefit of U.S. Provisional Application No. 62/482,450, filed on Apr. 6,2017, 62/482,891, filed on Apr. 7, 2017 and 62/550,711, filed on Aug.28, 2017, of all of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION 1. Technical Field

The present invention relates to the field of lithium ion batteries, andmore particularly, to electrolytes for lithium ion batteries.

2. Discussion of Related Art

With continued success in the portable electronic device market, Li-ionbatteries (LIBs) are of increasing interest for applications in electricand hybrid vehicles, surgical tools, and oil and gas drilling, etc., dueto their superior energy density and long cycle life.

However, current LIBs employ conventional liquid electrolytes based onorganic solvents, which poses a safety concern, especially at elevatedtemperatures. Specifically, the use of carbonate solvents such asethylene carbonate (EC), dimethyl carbonate (DMC), or diethyl carbonate(DEC) restricts battery operation to less than 60° C. due to theirvolatile and highly flammable nature. Moreover, when these solvents areused with Li salts, such as lithium hexafluorophosphate (LiPF₆), aresistive film forms on the electrode surface affording poor cycle life.These side reactions become more dominating at higher temperatures asthe rate of chemical reaction between the dissolved lithium salt andelectrolyte solvent increases.

SUMMARY OF THE INVENTION

The following is a simplified summary providing an initial understandingof the invention. The summary does not necessarily identify key elementsnor limit the scope of the invention, but merely serves as anintroduction to the following description.

One aspect of the present invention provides a lithium ion cellcomprising an electrolyte having at least one linear component and atleast one cyclic carbonate component, wherein the at least one cycliccarbonate component comprises at least 80% of fluoroethylene carbonate(FEC) and/or vinylene carbonate (VC), and wherein the electrolytecomprises at least 20% vol of FEC and/or VC and further comprises atleast one lithium salt.

One aspect of the present invention provides a lithium ion cellcomprising an anode and an electrolyte comprising at most 20% vol of atleast one ionic liquid additive, wherein the anode comprises a surfacelayer configured to bond at least a portion of the at least one ionicliquid additive.

One aspect of the present invention provides a pre-lithiation methodcomprising: mixing lithium powder with an ionic liquid, suspending themixture in an electrolyte, and introducing the suspension into the cell.

One aspect of the present invention provides a composite electrolyte forlithium ion cells, the composite electrolyte comprising solidelectrolyte particles coated by flexible ionic conductive material.

These, additional, and/or other aspects and/or advantages of the presentinvention are set forth in the detailed description which follows;possibly inferable from the detailed description; and/or learnable bypractice of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of embodiments of the invention and to showhow the same may be carried into effect, reference will now be made,purely by way of example, to the accompanying drawings in which likenumerals designate corresponding elements or sections throughout.

In the accompanying drawings:

FIG. 1A is a high-level schematic illustration of a metallizationprocess in lithium ion batteries according to the prior art.

FIG. 1B is a high-level schematic illustration of various anodeconfigurations, according to some embodiments of the invention.

FIGS. 2A-2D and 3A-3C schematically illustrate at least oneelectrolyte-buffering zone (mobile solid-electrolyte interface, MSEI) inan electrolyte, according to some embodiments of the invention.

FIG. 3D is a high-level schematic illustration of some of theconsiderations in determining an amount of ionic liquid additive,according to some embodiments of the invention.

FIGS. 4A and 4B are high-level schematic illustrations of animmobilized/mobilized SEI (I/MSEI) during charging and discharging,according to some embodiments of the invention.

FIG. 5A is a high-level schematic illustration of bonding moleculesforming a surface molecular layer on the anode and/or anode activematerial particles, according to some embodiments of the invention.

FIG. 5B is a high-level schematic illustration of non-limiting examplesfor bonding molecules, according to some embodiments of the invention.

FIG. 6 is a high-level schematic illustration of bonding moleculesforming a surface molecular layer on the anode and/or anode activematerial particles, according to some embodiments of the invention.

FIG. 7 is a high-level schematic illustration of bonding moleculesforming thick surface molecules layer on the anode and/or anode activematerial particles, according to some embodiments of the invention.

FIGS. 8A and 8B are high-level schematic illustrations of a lithium ioncell with the electrolyte during charging, according to some embodimentsof the invention.

FIG. 9 is a high-level flowchart illustrating a method, according tosome embodiments of the invention.

FIGS. 10A and 10B are non-limiting examples which indicate reversiblelithiation at the anode when using the ionic liquid additive accordingto some embodiments of the invention with respect to the prior art.

FIG. 11 is a high-level schematic block diagram of a prelithiationmethod applied to a lithium ion battery, according to some embodimentsof the invention.

FIG. 12 is a high-level flowchart illustrating a method, according tosome embodiments of the invention.

FIGS. 13A and 13B are high-level schematic illustrations of lithium ioncells, according to some embodiments of the invention. FIG. 13C is ahigh-level schematic illustration of prior art lithium ion cells.

FIGS. 14A and 14B are high-level schematic illustrations of the contactbetween an electrode and composite electrolyte, according to someembodiments of the invention.

FIG. 14C is a high-level schematic illustration of prior art contactbetween an electrode and a solid electrolyte.

FIGS. 14D-14H are high-level schematic illustrations of interfacesbetween electrode active material and electrolyte particles, accordingto some embodiments of the invention.

FIGS. 15A-15C are a high-level schematic block diagrams of variousproduction methods, according to some embodiments of the invention.

FIGS. 15D-15G are high-level schematic illustrations of interfacesbetween electrode active material and electrolyte particles, accordingto some embodiments of the invention.

FIG. 16 is a high-level flowchart illustrating a method, according tosome embodiments of the invention.

FIG. 17 is a high-level flowchart illustrating a method, according tosome embodiments of the invention.

FIGS. 18A-18D demonstrate the increased cell life for using electrolyteaccording to some embodiments of the invention, with respect to usingprior art electrolytes, in half cell experimental setting.

FIGS. 19A-19C demonstrate the increased performance for usingelectrolyte according to some embodiments of the invention, with respectto using prior art electrolytes, at high C rate in full cellexperimental setting.

FIGS. 20A-20J provide a range of examples for disclosed electrolytecompositions which outperform prior art electrolytes, according to someembodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, various aspects of the present inventionare described. For purposes of explanation, specific configurations anddetails are set forth in order to provide a thorough understanding ofthe present invention. However, it will also be apparent to one skilledin the art that the present invention may be practiced without thespecific details presented herein. Furthermore, well known features mayhave been omitted or simplified in order not to obscure the presentinvention. With specific reference to the drawings, it is stressed thatthe particulars shown are by way of example and for purposes ofillustrative discussion of the present invention only, and are presentedin the cause of providing what is believed to be the most useful andreadily understood description of the principles and conceptual aspectsof the invention. In this regard, no attempt is made to show structuraldetails of the invention in more detail than is necessary for afundamental understanding of the invention, the description taken withthe drawings making apparent to those skilled in the art how the severalforms of the invention may be embodied in practice.

Before at least one embodiment of the invention is explained in detail,it is to be understood that the invention is not limited in itsapplication to the details of construction and the arrangement of thecomponents set forth in the following description or illustrated in thedrawings. The invention is applicable to other embodiments that may bepracticed or carried out in various ways as well as to combinations ofthe disclosed embodiments. Also, it is to be understood that thephraseology and terminology employed herein is for the purpose ofdescription and should not be regarded as limiting.

The following analysis of lithium metallization and dendrite growth insome prior art anodes was used to define a problem which is solved byembodiments of the invention. The present disclosure is however notlimited by the disclosed analysis, and is in general not bound bytheory.

FIG. 1A is a high-level schematic illustration of a metallizationprocess in lithium ion batteries according to the prior art. Typicallithium ion batteries use graphite anodes 95 which receive lithium ions91 (passing through a carbonate-based electrolyte 85) in anintercalation process between graphite layers. The maximal capacity ofthe graphite is limited to approximately one lithium ion for every ca.six carbon atoms and is influenced by the solid-electrolyte interface(SEI) formed between anode 95 and electrolyte 85, typically on theintercalation basal planes (e.g., layers in the graphite materialbetween which the lithium ions intercalate). Such lithium ion batteriestypically have low charging and discharging rates due to limiting chargetransfer rates and limiting lithium ions diffusion rate into thegraphite anode. As shown schematically in illustration 90A in FIG. 1A,under low charging rates, the intercalation rate is higher than thelithium ion accumulation rate, resulting in proper intercalation 96 oflithium ions Li⁺ into graphite anode 95 as L^(˜0l), denotingapproximately neutral lithium atoms which receive electrons e from thegraphite and are intercalated in anode 95. The intercalation rate islimited by the Li⁺ supply rate. As the charging rate increases(schematic illustrations 90B, 90C, 90D represent gradually increasingcharging rate with respect to illustration 90A), the rate of incominglithium ions increases, and lithium ions accumulate on the surface (ofanode 95 or particles thereof, at the solid-electrolyte interface) asillustrated in 90B, with an accumulation rate that exceeds theintercalation rate of the lithium ions. As a result, reduction 97 of thelithium ions is carried out on the interface in addition to theintercalated lithium ions, as illustrated in 90C, which showsschematically the increasing flow of electrons to the interface withoutlithium ion intercalation in anode 95. Finally, as lithium ionaccumulation and reduction at the interface increase (as illustrated in90D), lithium metallization at the interface and dendrite growth 99commence and damage the cell. Additional considerations include volumechanges of the graphite electrode material, influences of anodeadditives, characteristics of the SEI and details of the charging anddischarging cycles. Without being bound by theory, FIG. 1A illustratesschematically a probable occurrence on the anode surface during slow 90Aand fast 90B-D charging, without the problematic catalytic reaction ofthe active material with the electrolyte (which complicates theschematically illustrated mechanism). While at low C rate the apparentdiffusion to the active material is fast enough to compensate themigration of the lithium ions through the electrolyte—at high C ratecharging, the migration through the electrolyte is faster than theapparent active material lithiation, which gives rise to metallizationprocess at the interface. Moreover, without proper protective coatingaround the active material metalloid, the active material-Li entity ishighly reactive toward the electrolyte, giving rise to catalyticreaction which decompose the electrolyte.

Electrolytes, anode material particles and methods are provided forimproving performance and enhancing the safety of lithium ion batteries.Electrolytes may comprise ionic liquid(s) as additives which protect theanode material particles and possibly bind thereto; and/or may comprisea large portion of fluoroethylene carbonate (FEC) and/or vinylenecarbonate (VC) as the cyclic carbonate component, and possibly ethylacetate (EA) and/or ethyl methyl carbonate (EMC) as the linearcomponent; and/or may comprise composite electrolytes having solidelectrolyte particles coated by flexible ionic conductive material.Ionic liquid may be used to pre-lithiate in situ the anode materialparticles. Disclosed electrolytes improve lithium ion conductivity,prevent electrolyte decomposition and/or prevents lithium metallizationon the surface of the anode.

Embodiments of the present invention provide efficient and economicalmethods and mechanisms for preventing lithium metallization in lithiumion batteries (LIBs) and thereby provide improvements and enhancingsafety in this technological field. It is suggested to use ionic liquidsas an additive to an organic, carbonate-based electrolyte 85 at lowconcentrations (e.g., up to ˜20% v/v) in order, e.g., to create amobilized SEI (MSEI) zone during charging and discharging. It is notedthat the MSEI may comprise a fluid layer of anions and/or cationsadjacent to the surface of the anode material particles, which isneither affixed to the anode material particles nor necessarily stableupon discharging of the cell. The surface layer of anions and/or cationsis not limited by referring to it herein as MSEI. These ionic liquidsmay be selected to be non-reactive or to have a very low reactivitytoward metallic lithium. A surface layer on the anode material particlesbonds (e.g., electrostatically and/or ionically) at least some of theionic liquid additive (an additive comprising ionic liquid) to form animmobilized layer that provides further protection at the interfacebetween the anode and the electrolyte, prevents metallization of lithiumon the anode and decomposition of the electrolyte.

Electrolytes, anodes, lithium ion cells and methods are provided forpreventing lithium metallization in lithium ion batteries to enhancetheir safety. Electrolytes comprise up to 20% ionic liquid additiveswhich form a mobile solid electrolyte interface (mobile SEI or MSEI dueto its functional operation in the cell, yet fundamentally differentfrom prior art SEI as the MSEI it is not part of nor necessarily affixedto the anode material particles, is fluid, and may dissolve into theelectrolyte upon discharging) during charging of the cell and preventlithium metallization and electrolyte decomposition on the anode whilemaintaining the lithium ion mobility at a level which enables fastcharging of the batteries. Anodes used with the present invention may bemetalloid-based, for example the anodes may include silicon, germanium,tin and/or aluminum (as used herein, “metalloid-based”) and/orlithium-titanate-based. The invention may also be applied for cellshaving graphite-based anodes and/or graphene-based anodes.

In certain embodiments, a surface layer on the anode material particlesmay be applied to bond (e.g., electrostatically and/or ionically) atleast some of the ionic liquid additive (an additive comprising ionicliquid) to form an immobilized layer (I/MSEI) that may provide furtherprotection at the interface between the anode and the electrolyte, mayprevent metallization of lithium on the former and decomposition of thelatter. It is emphasized that MSEI and/or I/MSEI may be createdindependently of each other, and possibly in addition to other types ofSEI which may be formed in or at the surface of the anode materialparticles.

Various embodiments comprise combinations of any of: using ionic liquidadditive(s) (additives comprising one or more ionic liquids) in theelectrolyte; applying a surface layer of molecules configured to bond atleast some of the anions and/or cations of the ionic liquid additive(s);prelithiating the electrodes with lithium powder suspended in the ionicliquid additive(s) or in different ionic liquid(s); using electrolyteswith a FEC/VC-based cyclic carbonate component; and/or using asemi-solid electrolyte with particles coated by flexible ionicconductive material, at least as part of the electrolyte—any of whichmay be implemented as disclosed herein, and optionally combined withembodiments of any of the combinations listed above.

Advantageously, some embodiments of the invention provide alternativeelectrolytes with superior thermal and chemical stability, which expandthe use of LIBs to a wider working temperature range withoutcompromising the electrochemical performance. Moreover, some embodimentsof the invention enable use of high energy metalloids and metals asanode active material, including C (graphite), as well as Si, Ge, Sn,Al, as disclosed e.g., in U.S. Pat. No. 9,472,804, filed on Nov. 12,2015 and U.S. Pat. No. 9,406,927, filed on Feb. 4, 2016; and in U.S.application Ser. No. 14/813,499 filed on Jul. 30, 2015 which areincorporated herein by reference in their entirety. Advantageously,disclosed MSEI may prevent breaking and/or provide a healing mechanismfor damage to fragile SEI layer(s) due to expansion and/or shrinkage ofthe anode. Moreover, disclosed embodiments reduce, to at least a partialextent during the cycle life of the LIB, decomposition of theelectrolyte solvent at the interface with the metalloid, which may actas a catalytic surface due to lithium metal species at the interfacesuch as lithium silicide (Li—Si).

FIG. 1B is a high-level schematic illustration of various anodeconfigurations, according to some embodiments of the invention. FIG. 1Billustrates schematically, in a non-limiting manner, a surface of anode100, which may comprise anode active material particles 110. Anodeactive material particles 110 may be of various types, at least some ofwhich comprising particles of metalloids such as silicon, germaniumand/or tin their alloys and/or mixtures, graphite, modified graphiteand/or graphene particles, and/or possibly particles of aluminum, leadand/or zinc, as well as forms of lithium titanate (LTO)—as well as anycombinations thereof. At least some of anode active material particles110 may possibly comprise composite particles 110B, e.g., core-shellparticles in various configurations. Anode active material particles 110may comprise particles at different sizes (e.g., in the order ofmagnitude of 100 nm, and/or possibly in the order of magnitude of 10 nmor 1I)—for receiving lithiated lithium during charging and releasinglithium ions during discharging. At least some of composite particles110B may be based on anode active material particles 110 as their cores.

Anodes 100 may further comprise binder(s) and additive(s) 108 as well asoptionally coatings 106 (e.g., conductive polymers, lithium polymers,conductive material such as carbon fibers and/or nanotubes etc.).Coatings 106 may be applied to patches or parts of the surface of anode100, and/or coatings 104 which may be applied onto anode materialparticles 110, and/or coatings 134 which may be configured as shellswith anode material particles 110 as cores, and/or conductive material139 such as carbon fibers and/or nanotubes may be configured tointerconnect anode material particles 110 and/or interconnect anodematerial particles 110 as cores of core-shell particles 110B. Activematerial particles 110 may be pre-coated by one or more coatings 106(e.g., by any of carbon coating, conductive polymers, lithium polymers,etc.), have borate and/or phosphate salt(s) 102A bond to their surface(possibly forming e.g., B₂O₃, P₂O₅ etc.), bonding molecules 116(illustrated schematically and disclosed in detail below) which mayinteract with electrolyte 105 (and/or ionic liquid additives thereto,see below) and/or various nanoparticles 102 (e.g., B₄C, WC, VC, TiN,possibly Sn and/or Si nanoparticles), forming modified anode activematerial particles 110A, which may be attached thereto in anodepreparation processes 103 such as ball milling (see, e.g., U.S. Pat. No.9,406,927, which is incorporated herein by reference in its entirety),slurry formation, spreading of the slurry and drying the spread slurry.For example, anode preparation processes 103 may comprise mixingadditive(s) 108 such as e.g., binder(s) (e.g., polyvinylidene fluoride,PVDF, styrene butadiene rubber, SBR, or any other binder),plasticizer(s) and/or conductive filler(s) with a solvent such as wateror organic solvent(s) (in which the anode materials have limitedsolubility) to make an anode slurry which is then dried, consolidatedand is positioned in contact with a current collector (e.g., a metal,such as aluminum or copper). Details for some of these possibleconfigurations are disclosed below.

Certain embodiments comprise anode material particles 110 comprising anyof silicon active material, germanium active material and/or tin activematerial, possibly further comprising carbon material, boron and/ortungsten. As non-limiting examples, anode material particles 110 maycomprise 5-50 weight % Si, 2-25 weight % B and/or 5-25 weight % W, and0.01-15 weight % C (e.g., as carbon nanotubes, CNT); anode materialparticles 110 may comprise 5-80 weight % Ge, 2-20 weight % B and/or 5-20weight % W, and 0.05-5 weight % C (e.g., as carbon nanotubes, CNT);anode material particles 110 may comprise 5-80 weight % Sn, 2-20 weight% B and/or 5-20 weight % W, and 0.5-5 weight % C (e.g., as carbonnanotubes, CNT); anode material particles 110 may comprise mixtures ofSi, Ge and Sn, e.g., at weight ratios of any of at least 4:1 (Ge:Si), atleast 4:1 (Sn:Si) or at least 4:1 (Sn+Ge):Si; anode material particles110 may comprise aluminum and/or any of zinc, cadmium and/or lead,possibly with additions of borate and/or phosphate salt(s) as disclosedbelow.

Certain embodiments comprise anode material particles 110 comprisingnanoparticles 102 attached thereto, such as any of B₄C, WC, VC and TiN,possibly having a particle size range of 10-50 nm and providing 5-25weight % of modified anode material particles 110A. Nanoparticles 102may be configured to form in modified anode material particles 110Acompounds such as Li₂B₄O₇ (lithium tetra-borate salt, e.g., via4Li+7MeO+2B₄C→2Li₂B₄O₇+C+7Me, not balanced with respect to C and O, withMe denoting active material such as Si, Ge, Sn etc.) or equivalentcompounds from e.g., WC, VC, TiN, which have higher affinity to oxygenthan the anode active material.

Certain embodiments comprise anode material particles 110 comprisingcoatings(s) 104 of any of lithium polymers, conductive polymers and/orhydrophobic polymers, such as e.g., any of lithium polyphosphate(Li_((n))PP or LiPP), lithium poly-acrylic acid (Li_((n))PAA or LiPAA),lithium carboxyl methyl cellulose (Li_((n))CMC or LiCMC), lithiumalginate (Li_((n))Alg or LiAlg) and combinations thereof, with (n)denoting multiple attached Li; polyaniline or substituted polyaniline,polypyrroles or substituted polypyrroles and so forth.

Any of anode material particles 110, 110A, 110B may be coated by thinfilms (e.g., 1-50 nm, or 2-10 nm thick) of carbon (e.g., amorphouscarbon, graphite, graphene, etc.) and/or transition metal oxide(s)(e.g., Al₂O₃, B₂O₃, TiO₂, ZrO₂, MnO etc.)

In certain embodiments, borate and/or phosphate salt(s) 102A maycomprise borate salts such as lithium bis(oxalato)borate (LiBOB,LiB(C₂O₄)₂), lithium difluoro(oxalato)borate (LiFOB, LiBF₂(C₂O₄)),lithium tetraborate (LiB₄O₇), lithium bis(malonato)borate (LiBMB),lithium bis(trifluoromethanesulfonylimide) (LiTFSI), or any othercompound which may lead to formation of borate salts (B₂O₃) on anodeactive material particles 110, including in certain embodiments B₄Cnanoparticles 102.

In certain embodiments, borate and/or phosphate salt(s) 102A maycomprise phosphate salts such as lithium phosphate (LiPO₄), lithiumpyrophosphate (LiP₂O₇), lithium tripolyphosphate (LiP₃O₁₀) or any othercompound which may lead to formation of phosphate salts (P₂O₅) on anodeactive material particles 110.

Certain embodiments comprise composite anode material particles 110Bwhich may be configured as core shell particles (e.g., the shell beingprovided by any of coating(s) 104 and possible modifications presentedabove). Different configurations are illustrated schematically indifferent regions of the illustrated anode surface, yet embodiments maycomprise any combinations of these configurations as well as any extentof anode surface with any of the disclosed configurations. Anode(s) 100may then be integrated in cells 150 which may be part of lithium ionbatteries, together with corresponding cathode(s) 87, electrolyte 105and separator 86, as well as other battery components (e.g., currentcollectors, electrolyte additives—see below, battery pouch, contacts,and so forth).

In certain embodiments, anode 110 may comprise conductive fibers 139which may extend throughout anode 100 (illustrated, in a non-limitingmanner, only at a section of anode 100) interconnect cores 110 andinterconnected among themselves. Electronic conductivity may be enhancedby any of the following: binder and additives 108, coatings 106,conductive fibers 139, nanoparticles 102 and pre-coatings 134, which maybe in contact with electronic conductive material (e.g., fibers) 139.

Lithium ion cell 150 may comprise anode(s) 100 (in any of itsconfigurations disclosed herein) made of anode material with compositeanode material such as any of anode material particles 110, 110A, 110B,electrolyte 120 (see below) and at least cathode 87 delivering lithiumions during charging through cell separator 86 to anode 100. Lithiumions (Li⁺) are lithiated (to Li^(˜0l), indicating substantiallynon-charged lithium, in lithiation state, see e.g., FIGS. 2B and 2Dbelow)) when penetrating the anode material, e.g., into anode activematerial cores 110 (possibly of core-shell particles 110B). Any of theconfigurations of composite anode material and core-shell particles 110Bpresented below may be used in anode 100, as particles 110B areillustrated in a generic, non-limiting way. In core-shell particleconfigurations 110B, the shell may be at least partly be provided bycoating(s) 134, and may be configured to provide a gap 137 for anodeactive material 110 to expand 138 upon lithiation. In some embodiments,gap 137 may be implemented by an elastic or plastic filling materialand/or by the flexibility of coating(s) 134 which may extend as anodeactive material cores 110 expands and thereby effective provide room forexpansion 138, indicated in FIG. 1B schematically, in a non-limitingmanner as gap 137. Examples for both types of gaps 137 are providedbelow, and may be combined, e.g., by providing small gap 137 andenabling further place for expansion by the coating flexibility.

Anode material particles 110, 110A, 110B, anodes 100 and cells 150 maybe configured according to the disclosed principles to enable highcharging and/or discharging rates (C-rate), ranging from 3-10 C-rate,10-100 C-rate or even above 100 C, e.g., 5 C, 10 C, 15 C, 30 C or more.It is noted that the term C-rate is a measure of charging and/ordischarging of cell/battery capacity, e.g., with IC denoting chargingand/or discharging the cell in an hour, and XC (e.g., 5 C, 10 C, 50 Cetc.) denoting charging and/or discharging the cell in 1/X of anhour—with respect to a given capacity of the cell.

Examples for electrolyte 105 may comprise liquid electrolytes such asethylene carbonate, diethyl carbonate, propylene carbonate, VC, FEC,EMC, DMC and combinations thereof and/or solid electrolytes such aspolymeric electrolytes such as polyethylene oxide, fluorine-containingpolymers and copolymers (e.g., polytetrafluoroethylene), andcombinations thereof. Electrolyte 105 may comprise lithium electrolytesalt(s) such as LiPF₆, LiBF₄, lithium bis(oxalato)borate, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, LiAsF₆, LiC(CF₃SO₂)₃, LiClO₄, LiTFSI, LiB(C₂O₄)₂,LiBF₂(C₂O₄)), tris(trimethylsilyl)phosphite (TMSP), and combinationsthereof. Ionic liquid(s) 135 may be added to electrolyte 105 asdisclosed below.

Electrolytes 120 disclosed below (e.g., in FIGS. 13A-16 and relateddescription) may be configured to operate with any of the disclosedanode embodiments, and the electrolyte production process may possiblybe incorporated in the anode production process as disclosed above.

In certain embodiments, cathode(s) 87 may comprise materials based onlayered, spinel and/or olivine frameworks, and comprise variouscompositions, such as LCO formulations (based on LiCoO₂), NMCformulations (based on lithium nickel-manganese-cobalt), NCAformulations (based on lithium nickel cobalt aluminum oxides), LMOformulations (based on LiMn₂O₄), LMN formulations (based on lithiummanganese-nickel oxides) LFP formulations (based on LiFePO₄), lithiumrich cathodes, and/or combinations thereof.

It is explicitly noted that in certain embodiments, cathodes and anodesmay be interchanged as electrodes in the disclosed cells, and the use ofthe term anode is not limiting the scope of the invention. Any mentionof the term anode may be replaced in some embodiments with the termselectrode and/or cathode, and corresponding cell elements may beprovided in certain embodiments. For example, in cells 150 configured toprovide both fast charging and fast discharging, one or both electrodes100, 87 may be prepared according to embodiments of the disclosedinvention. Separator(s) 86 may comprise various materials, e.g.,polymers such as any of polyethylene (PE), polypropylene (PP),polyethylene terephthalate (PET), poly vinylidene fluoride (PVDF),polymer membranes such as a polyolefin, polypropylene, or polyethylenemembranes. Multi-membranes made of these materials, micro-porous filmsthereof, woven or non-woven fabrics etc. may be used as separator(s) 86,as well as possibly composite materials including, e.g., alumina,zirconia, titania, magnesia, silica and calcium carbonate along withvarious polymer components as listed above.

FIGS. 2A-2D and 3A-3C schematically illustrate at least oneelectrolyte-buffering zone 130 (MSEI) in an electrolyte 105, accordingto some embodiments of the invention. Electrolyte-buffering zone(s) 130may be formed by an ionic liquid additive 135 (an additive comprisingionic liquid—ionic liquids comprise one or more salt(s) which are liquidbelow 100° C., or even at room temperature or at lowertemperatures-sometimes called “fused salts”) and is illustratedschematically as an accumulation of anions 131 and cations 132, whichprovides separation between organic electrolyte 85 (as main component ofelectrolyte 105) and anode 100 (illustrated e.g., with respect to anodematerial particle 110) and may be configured to further regulate lithiumion movement from electrolyte 105 to anode 100 (illustrated e.g., withrespect to anode material particles 110). It is noted that shapes andsizes of anions 131 and cations 132 are used for illustration purposes,anions 131 and cations 132 may have various relative sizes and shapes,depending on the specific ionic liquid(s) which are selected as ionicliquid additive 135. For example, anions 131 and/or cations 132 may berelatively large, e.g., larger than lithium ions 91 and/or significantlylarger than lithium ions 91 (e.g., larger than lithium ions by at least10%, 25%, 50% or more, possibly by at least 100%, 200%, 500% or evenmore, in either volume or radius) to establish a gradient in physicaland/or chemical characteristics in region 130 and possibly provide aninterphase transition between electrolyte 105 and anode 100 (illustratede.g., with respect to anode material particles 110) that enhances thestabilization of transition region and prevents lithium ion accumulationand/or metallization and dendrite growth. Anions 131 may be selected toprovide negative electric charge in the region of lithium ions 91 movingtowards anode 100 (illustrated e.g., with respect to anode materialparticles 110), which somewhat, yet not fully, reduces the positivecharge of lithium ions 91 to δ+ (e.g., by physical proximity, such asthrough, e.g., electrostatic and/or ionic interactions, and not by achemical bond). The relative sizes of anions 131 and cations 132 mayvary—anions 131 and cations 132 may have a similar size or one of anions131 and cations 132 may be larger than the other. Mixtures of differentionic liquid additives 135 may have different size relations betweentheir anions 131 and cations 132.

In certain embodiments, electrolyte 105 may comprise ionic liquidadditive 135 (e.g., at 20%, 10%, 5%, 2%, 1% v/v or any other volume partsmaller than 20%), added to carbonate-based electrolyte 85, which isselected to at least partially provide anions 131 and/or cations 132 tobuild electrolyte-buffering zone(s) 130. For example, ionic liquidadditive 135 may comprise acidic groups which are selected to be anionicin the environment of lithium ions 91. Anions 131 and/or cations 132 maybe relatively large to form a barrier which reduces the approachingspeed of lithium ions 91 and which locally increases the resistance ofelectrolyte-buffering zone(s) 130 to lithium ions 91 to prevent orattenuate accumulation of lithium ions 91 at the surface of anode 100(illustrated e.g., with respect to anode material particles 110).

Ionic liquid additive 135 may be selected to be not reactive in thecell, not to be reactive with lithium metal (e.g., not decompose in thepresence of lithium metal) and not to intercalate with active material110 of anode 100. The ionic strength and lithium ion mobility may beselected to appropriate values and the ionic conductivity may becontrolled in a better way than a single component electrolyte 85.Moreover, ionic liquid additive 135 may be selected to have large volumeanions 131 and cations 132 (illustrated schematically in FIGS. 2A-C).Advantageously, using ionic liquid additive 135 in the cell overcomes aprior art need to balance the risk of lithium metallization (requiringlow lithium accumulation concentration at the anode surface) with theability to fast charge the battery over a large number of cycles(requiring high lithium conductivity and mobility).

FIG. 2A illustrates schematically the situation prior to application ofan electrical field in the vicinity of anode 100 (illustrated e.g., withrespect to anode material particles 110) and FIGS. 2B and 2D illustrateschematically the situation during application of an electrical field inthe vicinity of anode 100 (e.g., anode material particles 110). In theformer case (FIG. 2A), the dispersion of anions 131 and cations 132 ofionic liquid additive 135 in electrolyte 105 may be essentiallyhomogenous; while during application of an electrical field in thevicinity of anode 100 (e.g., of anode material particles 110), anions131 and cations 132 of ionic liquid additive 135 accumulate in zone 130in electrolyte 105 which is adjacent to the active material surface ofanode 100. Without being bound to theory, anions 131 and cations 132 areheld adjacent to anode 100 by electrostatic forces, without reactingchemically with the active material of anode 100. Electrolyte-bufferingzone(s) 130 may vary in the degree to which anions 131 and cations 132are ordered, typically the degree of order decreases with increasingdistance from the anode surface as the electrostatic forces becomeweaker.

FIG. 2C is a high-level schematic illustration of non-limiting examplesfor ion sizes and shapes of ionic liquid additive 135, according to someembodiments of the invention. Cations 132 and anions 131 may havevarious sizes and shapes, e.g., cations 132 may be larger than anions131, cations 132 may be smaller than anions 131, cations 132 may beabout the same size as anions 131, and/or combinations of cations 132and anions 131 with different size relations may be used together asionic liquid additive 135. Cations 132 may be elongated or spherical,anions 131 may be elongated or spherical and/or combinations of cations132 and anions 131 with different shapes may be used together as ionicliquid additive 135. At least one of cations 132 and anions 131 may belarger than lithium ions 91, as illustrated schematically in FIG. 2C.Any of these combinations may be used in any of the disclosedembodiments, and the specific shapes and sizes of cations 132 and anions131 illustrated in FIGS. 2A, 2B, 2D, 3B and 3C may be replaced with anyof the shapes and sizes illustrated in FIG. 2C, and are non-limiting.

FIG. 2D illustrates schematically possible different thicknesses ofelectrolyte-buffering zone(s) 130 and the spreading of the charge withdistance from anode 100 and/or anode material 110, which may beconfigured according to performance requirements, and may vary underdifferent specifications. For example, electrolyte-buffering zone(s),MSEI 130, may comprise 1, 2, 4 or more layers of cations 132 and anions131, depending on electrolyte composition, types of ionic liquidadditive 135, sizes of ions, level of charge etc.

Ionic liquid additive 135 may be selected to enable lithium iontransport therethrough while partly reducing the lithium ions and keepthem in a partly charged form Li^(δ+) in zone 130.

FIG. 3A schematically illustrates at least one electrolyte-bufferingzone 130 (MSEI) in an electrolyte 105, which is configured to provide amobility and charge gradient 119 (indicated schematically by the taperedarrows) having surrounding electric charge 136 (illustratedschematically as a non-specific symbol), according to some embodimentsof the invention. Mobility and charge gradient 119 reduces and slowslithium ions 91 entering zone 130 in a gradual manner (indicatedschematically by Li^(δ+), with the partial charge of the lithium ionschanging gradually within zone 130) until they reach lithiation (e.g.,intercalation in case of graphite particles) in anode 100. Gradient 119may be configured to enable modification of the interface (the areawhere the two immiscible phase surfaces of anode and electrolyte arecoming in contact with each other) into an interphase region 130 havinga gradual change of parameters which gradually reduces the activationenergy of the reduction reaction of the lithium ions, and furtherprevents metallization of lithium and dendrite growth. MSEI zone 130helps smoothen the lithium ion transport into the active material forfull reduction and lithiation (to Li^(˜0l)). The resulting ionic liquidlayer 130 reduces the probability of both lithium metallization anddecomposition of the organic solvent (electrolyte 85) at themetalloid-lithium surface. Once the electrical field stops (e.g., at theend or interruption of the charging), ionic liquid 135 may slowlydiffuse to form homogenous electrolyte 105. It is explicitly noted,however, that ionic liquid additive 135 may be used in cells havingmetalloid-based and/or graphite-based anodes (either possibly coatedand/or pre-coated).

FIG. 3B schematically illustrates at least one electrolyte-bufferingzone 130 (MSEI) in an electrolyte 105, which is configured to fillpossible cracks 114 appearing in a surface 112 of anode, e.g., due tocracking of a surface layer 115 (which may be e.g., a SEI, a coatingand/or an anode buffering zone, e.g., as disclosed in the applicationscited above) upon expansion and contraction of anode 100, according tosome embodiments of the invention.

Under various configurations of anodes 100, cracks may appear in surfacelayer 115 of anode, which may comprise or support a SEI (which may bebrittle), a coating and/or a buffering zone. Such cracks may enablerenewed contact between the anode material and/or metal lithium andelectrolyte 85, or increase the surface area available for suchcontact—causing further electrolyte decomposition and possible sites forlithium metallization. Ionic liquid additive 135 may be configured tofill in such cracks 114 (illustrated schematically in FIG. 3B) once anelectric field is applied, or possibly also after the electric field isapplied, to reduce the extent of, or prevent, cracks 114 from enhancingelectrolyte decomposition and lithium metallization. Anode 100 may becoated and/or pre-coated by a full or partial coating (e.g., a polymercoating, a nanoparticles coating, etc., e.g., on as at least part ofsurface layer 115, e.g., as disclosed in the applications cited above,and see FIG. 1B), which may be applied before and/or after anodeformation (pre- and/or post-coating). Ionic liquid additive 135 may beconfigured to fill in cracks or uncoated surface areas as explainedabove, including possible exposed surfaces in the coating resulting fromthe expansion and contraction during cell cycles (see also FIG. 3C).

FIG. 3C schematically illustrates the ability of mobilized SEI (MSEI)layer 130 to rearrange and maintain itself as electrolyte-bufferingzone(s) 130 upon expansion and contraction of anode 100, according tosome embodiments of the invention. Expansion 100A and contraction 100Bare illustrated schematically by the respective arrows, the indicationof amount of intercalated lithium (denoted Li^(˜0l)) which correspond to(partly) discharged state 101A and (partly) charged state 101B, theschematically illustrated movement of anode surface 112 from 112A to112B and expansion of surface layer 115 from 115A to 115B. Ionic liquidadditive 135, being a liquid, accommodates itself easily (illustratedschematically by MSEI layers 130A, 130B) upon expansion 100A andcontraction 100B by re-arrangement of cations 132 and anions 131 (fromschematically illustrated arrangement 132A, 131A to 132B, 131B,corresponding to MSEIs 130A, 130B).

Without being bound by theory, the mechanism of MSEI formation may beboth concentration and kinetically controlled, e.g., the more ionicliquid additive 135 is separated from electrolyte 105, the faster mobileSEI layer 130 forms; while an increase of the concentration of ionicliquid additive 135 may reduce the ionic mobility through MSEI 130. Theconcentration of ionic liquid additive 135 may thus be selected tobalance reduced ionic mobility by higher concentration with possibleelectrolyte decomposition on the active material-electrolyte interfacewhich may be enabled by too low concentrations of ionic liquid additive135 (which forms MSEI 130 too slowly). Moreover, using ionic liquidadditive 135 may maintain or enhance the ionic strength, withoutcompromising the ionic mobility by increasing the ionic resistance, byenabling a reduction of the lithium salt (e.g., LiPF₆) concentration,which also further reduces the probability for metallization.

In embodiments, the ionic liquid additive contains a charged nitrogenatom. Non-limiting examples of ionic liquid additives 135 include,without limitation, any of the following and their combinations:1-butyl-1-methylpyrrolidinium as cation 132 andbis(trifluoromethanesulfonyl)imide as anion 131 (melting point −6° C.);1-butyl-3-methylimidazolium as cation 132 andbis(trifluoromethanesulfonyl)imide as anion 131 (melting point −4° C.);1-butyl-3-methylimidazolium as cation 132 and bis(fluorosulfonyl)imideas anion 131 (melting point −13° C.);N,N-Diethyl-N-methyl-N-propylammonium as cation 132 andbis(fluorosulfonyl)imide as anion 131; and N-propyl-N-methylpiperidiniumas cation 132 and bis(trifluoromethanesulfonyl)imide as anion 131.Certain embodiments comprise ionic liquids which are derived from thesecombinations, i.e., having various substituents. As illustrated in theexamples above, ionic liquid additives 135 may be based onsulfonylimides as anions 131 and on piperidinium derivatives as cations132, referred to below as ionic liquids based on sulfonylimides andpiperidinium derivatives.

Advantageously, certain embodiments use, as ionic liquid additives 135,ionic liquids having a negligible vapor pressure and which are liquid atroom temperature, a wide electrochemical potential window (e.g., up to5.0 V in ionic liquids based on sulfonylimides and piperidiniumderivatives), and structural stability across a large temperature range(e.g., up to 385° C. in ionic liquids based on sulfonylimides andpiperidinium derivatives). For example, the ionic liquids may havemelting temperatures of 10-20° C., 0-10° C., or possibly even <0° C.,e.g., 0-−4° C., −4°-−13° C., or even lower, e.g., below −20° C., havingmelting points down to −40° C., as non-limiting examples. The lithiumion conductivity in certain ionic liquids based on sulfonylimides andpiperidinium derivatives at room temperature may be, for example,between 1-20 mS/cm (at 20° C.), in some embodiments, between 1.4-15.4mS/cm (at 20° C.), wherein exact values can be provided according torequirements.

The use of ionic liquids as additive 135 solves prior art problems inattempting to use ionic liquids as electrolytes 85, such as their highviscosity and low Li-ion conductivity at room temperature and reducedcathodic stability. Their use as additives 135 (e.g., up to 20% vol ofelectrolyte 105, the rest comprising electrolyte 85) mitigates theirprior art disadvantages and utilizes their advantageous property exactlywhere needed, e.g., at the anode-electrolyte interface. Moreover, theuse of ionic liquids based on sulfonylimides and piperidiniumderivatives with C (e.g., graphite), or metalloid (e.g., Si, Sn, Ge orAl)-based anodes solves prior art problems of co-intercalation of thepiperidinium cations along with the Li-ion in graphite-based electrodesat lower potentials during the charge-discharge process—asmetalloid-based anodes do not co-intercalate the piperidinium cations.Nevertheless, some embodiments comprise using disclosed electrolytes 105with ionic liquid additives 135 in lithium ion cells employing graphiteanodes.

FIG. 3D is a high-level schematic illustration of some of theconsiderations in determining an amount of ionic liquid additive 135,according to some embodiments of the invention. The considerations areshown schematically as the cross-hatched arrows. The amount of ionicliquid additive 135 in electrolyte 105, may be determined according tothe specific parameters and characteristics of cells 150 (see schematicFIGS. 8A and 8B below) such as the type of the anode active materialfrom which anode material particles 110 are made, the expansioncoefficient of the anode active material, the expected and/or specifiedextent of expansion of anode material particles 110 during operation(see, e.g., FIG. 3C), expected level of cracking in the SEI (see, e.g.,FIG. 3B) parameters of anode material particles 110 such as dimensions(diameter, volume, surface area), relative amount and number in anode100, anode porosity, coatings of particles 110 and/or other materials inanode 100 (see e.g., FIG. 1B), as well as parameters of electrolyte 105and its components, such as their molecular weight, density, reactivitytowards the anode active material, ionic conductivity and the amount ofelectrolyte, and clearly according to the specific parameters andcharacteristics of ionic liquid additive(s) 135 such as size, molecularweight, form, electrostatic characteristics of the respective cation(s)132 and anion(s) 131 (see, e.g., FIG. 2C), and the expected and/orspecified number of layers of ionic liquid additive(s) 135 on anodematerial particles 110 during charging (see, e.g., FIGS. 2B and 2D). Afew (non-limiting) of these considerations are illustrated in FIG. 3Dschematically by the cross-hatched arrows, namely the type, expansioncharacteristics and dimensions of anode material particles 110, thenumber of layers of cations 132 and anions 131 of ionic liquid additive135 which take part in MSEI 130 (indicated schematically as 130(1 . . .n), for non-limiting n=2 and n=4), which may further depend, among otherparameters on the expansion state of anode material particles 110 and onother ingredients of electrolyte 105, and the shape, size, andelectrostatic characteristics of cation(s) 132 and anion(s) 131 of ionicliquid additive(s) 135.

For example, in quantitative, non-limiting examples, assuming germaniumas anode active material which may reach 270% expansion upon lithiation,and particle diameter of 100 nm, the surface area per particle uponlithiation may increase from ca. 31,000 nm² to ca. 61,000 nm². Dependingon the number of required ionic liquid additive molecular layers 130(1 .. . n) and on the molecule area, the number of required ionic liquidmolecules for covering the overall surface area of the anode activematerial particles may be calculated. For example, in a non-limitingcalculation assuming three layers (n=3) at the maximal expansion of theparticles and N,N-Diethyl-N-methyl-N-propylammonium (cation 132) andbis(fluorosulfonyl)imide (anion 131) as ionic liquid additive 135(relating to cations 132 thereof for molecule size calculation—ca. 0.3nm²), ca. 620,000 molecules are required per particle, or ca. 10⁻¹⁸ molionic liquid additive 135. Proceeding with estimating the overall numberof particles, their mass, the molar weight of the electrolyte and theionic liquid additive, the volume % of ionic liquid additive 135 may becalculated. For example, for 70% active material in the anode, thenumber of particle was estimated as ca. 5·10¹¹, requiring ca. 5·10⁻⁷ molof ionic liquid additive 135 which is equivalent to ca. 0.05 mol/literionic liquid additive in electrolyte 105 (assuming electrolyte 85comprising FEC:DMC (3:7) and 2% VC—FEC denoting fluorinated ethylenecarbonates, DMC denoting dimethyl carbonate and VC denoting vinylenecarbonate), or ca. 1.2% vol of ionic liquid additive 135 in electrolyte105. Clearly, any adaptation of electrolyte 105 with respect to itsingredients, as well as any modification of the required number oflayers 130 (e.g., n=1, 2, 5, 10 etc.) in expanded state yields differentpercentage, which may be taken into account when preparing electrolyte105. For example, in certain embodiments, ionic liquid additive 135concentration of 0.4% vol may be sufficient to provide one layer 130 atmost expanded state of anode material particles 110 which corresponds tofull lithiation. In other embodiments, lower percentage of activematerial in the anode may require using less ionic liquid additive 135,but not necessarily at a linear relation.

Similar calculations may be carried out for other anode active materialssuch as silicon (which may reach 400% expansion upon lithiation), tin(which may reach 330% expansion upon lithiation), alloys and/or mixturesthereof (with or without germanium) which may have intermediateexpansion coefficients, and even less expanding anode active materialssuch as graphite (which typically expands by 10% upon lithiation), LTO(lithium titanate oxide) with minimal expansion (0.02%). Similarcalculations may be carried out with respect to particle sizes andsurface area, various types of ionic liquid 135 and various types ofelectrolyte 105, which are disclosed herein. The calculations presentedabove may be modified to determine the required concentration of ionicliquid additive 135 in electrolyte 105 using the correspondingmaterials.

Concluding from the examples presented above, the concentration of ionicliquid additive 135 in electrolyte 105 may be determined according tothe disclosed guidelines and may vary greatly from embodiment toembodiment. While large concentrations of up to 20% may be used, someembodiments may comprise lower concentrations of 1% vol, 1-0.1% vol,2-0.1% vol, or possibly even concentrations lower than 0.1%.

FIGS. 4A and 4B are high-level schematic illustrations of animmobilized/mobilized SEI (I/MSEI) during charging and discharging,according to some embodiments of the invention. In certain embodiments,surface functionalization of the anode active material may enhance thefunctionality of MSEI 130, e.g., by increasing the affinity of ionicliquid 135 to the active material—electrolyte interface, and protect theinterface from direct interaction with the organic solvent (ofelectrolyte 85). Surface functionalization may be applied by anodecoatings or pre-coatings and/or by additional modifications of surface112 of anode 100 (e.g., of anode material particles 110) and/or of theactive material on anode surface 112. For example, a chemically bondedcoating 145 of bonding molecules 116 such as large volume salt(s) onactive material surface 112 may be used to keep some of ionic liquid 135on surface 112 and reduce the probability of the organic solventdecomposition prior to the MSEI re-arrangement at the interface. FIGS.4A and 4B schematically illustrate this effect by the retainment of atleast some of cations 132 bonded to surface 112 even when the cell isnot charged. FIGS. 4A and 4B schematically illustrate anode 100 (e.g.,anode material particles 110) during charging 101C and discharging (orno charging, 101D) with ionic liquid additive 135 building MSEI 130 incharging state 101C, which may comprise an immobilized section 140A anda mobile section 140B, the former remaining in discharging state 101Dbonded or associate with anode surface while the latter returning intoelectrolyte 105 in discharging state 101D. Coating 145 may represent alayer in which bonding molecules 116 are associated with an anodecoating and/or attached to anode 100. Cations 132C and possibly anions131C which stay bonded to bonding molecules 116 (immobilized section140A of ionic liquid additive 135) are denoted differently from cations132B and anions 131B which stay in electrolyte 105 (mobile section 140Bof ionic liquid additive 135), to illustrate that a part (or possiblyall) of electrolyte additive 135 is immobilized onto layer 145 of anode100 during operation of the cell. Immobilized layer 140A at theinterface may have a better affinity to ionic liquid 135 and lessaffinity toward organic solvent of electrolyte 85, and therefore keepthe organic solvent away from the interface and reduce the probabilityfor its decomposition.

In some embodiments, the bonding of ions of ionic liquid additive(s) 135may involve bonding cations 132 or possibly anions 131 by bondingmolecules 116 as the layer closest to surface 112. The bonding may becarried out during one or more first charging and discharging cycles ofcell 150. In certain embodiments, the bonding of cations 132 and/oranions 131 may be carried out, at least partially, on active material110 itself, even before the first charging cycle. The bonding of theionic liquid to bonding layer 145 may be electrostatic and/or salt-like(ionic). In certain embodiments, the bonding may be at least partlycovalent. The bonding may involve any number of ionic layers, typicallya few layers, possibly providing a salt layer which isolates the organicsolvent used for electrolyte 85 at least from active material 110 ofanode 100.

Bonding molecules 116 may be ionic or have electron rich groups such assodium aniline sulfonate. Bonding molecules 116 may comprise lithiumcations and/or possibly magnesium cations, the latter possibly when theanode material is graphite. Non-limiting examples for bonding molecules116 comprise lithium alkylsulfonate, poly(lithium alkylsulfonate),lithium sulfate, lithium phosphate, lithium phosphate monobasic,alkylhydroxamate salts and their acidic forms (e.g., lithium sulfonicacid, LiHSO₄, instead of lithium sulfonate, Li₂SO₄). In case of aluminumas anode material, bonding molecules 116 may comprise lithium cationsand/or aluminum cations. The lithium in the following examples may thusbe replaced in some embodiments by magnesium and/or aluminum. In case ofgraphite anodes, a wide range of activation techniques which yieldoxidized graphite may be used to enhance chemical bonding of molecules116 (e.g., using halides or alkoxides). See below an elaboration ofbonding molecules 116 and their characteristics.

The chemical bonding of molecules 116 to anode 100 (e.g., to anodematerial particles 110) may be carried out, for example, in the anodeslurry solution and/or in dry ball milling with anode materialparticles. The bonding mechanism may comprise, e.g., reaction(s) of thelithium sulfonates and/or salts with metal oxides, releasing the oxideand creating a direct chemical bond to metalloid surface 112, where thelithium cation remain partly charged (Li^(δ+)) in the metalloid. Forexample, using a large volume salt with an additional anion group asbonding molecules 116 may create a salt surface 145 on metalloidmaterial 110, which can both protect the interface and co-operate withionic liquid additive 135 in electrolyte 105. Layer 145 may bind astationary portion of ionic liquid additive 135 on metalloid surface 112while the rest of ionic liquid additive 135 is mobilized in electrolyte105, providing a hybrid ionic liquid additive which is partly bonded andpartly free in electrolyte 105. Stationary portion 140A may increase there-ordering rate of ionic liquid additive 135 on surface 115 duringcharging (101C), help repel organic electrolyte 85 from the interfaceand hence reduce the probability for the decomposition of the organicsolvent. Non-limiting examples for bonding molecules 116 include largeanionic salts or their acids which may be selected to sterically repelthe smaller organic carbonates solvents (of electrolyte 85) from activematerial surface 112. Layer 145 and stationary portion 140A of ionicliquid additive 135 on metalloid surface 112 may be highly effectiveduring the initial charging, and enable or support the building of astable SEI during the formation cycle(s) which protects surface 112 andanode 100 during later operation, and prevent decomposition ofelectrolyte on anode 100 as well as lithium metallization thereupon.

The resulting SEI may be modified toward enhanced stability and bepossibly provided with self-healing mechanisms through layer 145 andstationary portion 140A of ionic liquid additive 135.

In some embodiments, bonding molecules 116 are represented by formula I:

wherein:each Z is independently selected from aryl, heterocycloalkyl, crownetheryl, cyclamyl, cyclenyl, 1,4,7-Triazacyclononanyl, hexacyclenyl,cryptandyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl,chrysenyl, triphenylenyl pyrenyl and pentacenyl;R¹ is [C(L¹)₂]_(q) ¹-R¹⁰¹;each L¹ is independently selected from H, F and R¹⁰¹;R², R³, R⁴, R⁵, R⁶ and R¹⁰¹ are each independently selected from CO₂H,CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂,PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR,SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃, and Si(OR)₃;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, andbenzyl;each M¹ is independently Li, Na, K, Rb or Cs:each M² is independently Be, Mg, Ca, Sr or Ba;T¹ and T² are each independently absent, or selected from H, CO₂H,CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂,PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR,SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃, and Si(OR)₃;m¹, m², m³, m⁴, m⁵, and m⁶ are each independently an integer between0-6;n¹ is an integer between 1-10;q¹ is an integer between 0-10; andZ is connected to any of R¹-R⁶, T¹-T² or to any neighboring repeatingunit in any possible substitution position and via one or more atoms,

In some embodiments, bonding molecules 116 are represented by formulaII:

wherein:R⁷ is [C(L²)₂]_(q) ²-R¹⁰²;each L² is independently selected from H, F and R¹⁰²;R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹⁰² are each independently selected fromCO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂,PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR,SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano andSi(OR)₃;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, andbenzyl;each M¹ is independently Li, Na, K, Rb or Cs;each M² is independently Be, Mg, Ca, Sr or Ba;m⁷, m⁸, m⁹, m¹⁰, m¹¹ and m¹² are each independently an integer between0-6; andq² is an integer between 0-10.

In some embodiments, bonding molecules 116 are represented by formulaIII:(L³)₃C—R¹⁰³  (III)whereinR¹⁰³ is [C(L⁴)₂]_(q) ³-R¹⁰⁵;each L³ is independently selected from H, F and R¹⁰⁴;each L⁴ is independently selected from H, F and R¹⁰⁶;R¹⁰⁴, R¹⁰⁵, and R¹⁰⁶ are each independently selected from CO₂H, CO₂M¹,CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H,PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃ and Si(OR)₃;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, orbenzyl;each M¹ is independently Li, Na, K, Rb or Cs;each M² is independently Be, Mg, Ca, Sr or Ba; andq³ is an integer between 0-10.

In some embodiments, bonding molecules 116 are represented by formulaIV:

wherein:X¹ and X² are each independently selected from S, O and CH₂;R¹³ and R¹⁴ are each independently selected from CO₂H, CO₂M¹, CO₂R,SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M²,C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃ and Si(OR)₃;each M¹ is independently Li, Na, K, Rb or Cs;each M² is independently Be, Mg, Ca, Sr or Ba;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, orbenzyl; andn², n³, n⁴ and n⁵ are each independently an integer between 0-10,

In some embodiments, bonding molecules 116 are represented by formula V:

wherein:X³ and X⁴ are each independently selected from S, O and CH₂;R¹⁵ and R¹⁶ are each independently selected from CO₂H, CO₂M¹, CO₂R,SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M²,C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃ and Si(OR)₃;each M¹ is independently Li, Na, K, Rb or Cs;each M² is independently Be, Mg, Ca, Sr or Ba;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, orbenzyl; andn⁶, and n⁷ are each independently an integer between 0-10

In some embodiments, bonding molecules 116 are represented by formulaVI:

wherein:each R¹⁷ is independently selected from CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹,PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂,NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano, CF₃ and Si(OR)₃;T³ and T⁴ are each independently selected from H, CO₂H, CO₂M¹, CO₂R,SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M²,C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃ and Si(OR)₃;each M¹ is independently Li, Na, K, Rb or Cs;each M² is independently Be, Mg, Ca, Sr or Ba;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, orbenzyl; andn⁸ is an integer between 2-10000.

In some embodiments, bonding molecules 116 are represented by formulaVII:

wherein:R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are each independently selected from CO₂H,CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂,PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR,SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃and Si(OR)₃;T⁵ and T⁶ are each independently selected from H, CO₂H, CO₂M¹, CO₂R,SO₃H, SO₃M¹, PO₃H², PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M²,C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano,CF₃ and Si(OR)₃;each M¹ is independently Li, Na, K, Rb or Cs:each M² is independently Be, Mg, Ca, Sr or Ba;each R is independently selected from methyl, ethyl, isopropyl,n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, andbenzyl;

-   -   n⁹ is an integer between 20-10000; and        m⁷, m⁸, m⁹, m¹⁰, m¹¹ and m¹² are each independently an integer        between 0-5.

In some embodiments, bonding molecules 116 may be polymers, possiblycrosslinked with inorganic crosslinkers. Non limiting examples ofpolymers include polymers represented by formula VI, polyvinylalcohol(PVA), polymethylmetacrylate (PMMA), polyacrylic acid (PAA),polyethylene glycol (PEG), polyvinylsulfonic acid andpolyvinylpyrrolidone (PVP), or any combination thereof. Non limitingexamples of inorganic crosslinkers include boron (B) oxides, zirconiumcomplexes and tetralkoxysilanes or any combination thereof. Non limitingexamples of boron (B) oxides include boric acid (H₃BO₃), salts oftetraborate (B₄O₇ ²⁻) and boron trioxide (B₂O₃). In some embodiments,salts of tetraborate (B₄O₇ ²⁻) are selected from the anion tetraborateand a cation of alkali metal or alkaline earth metal, aluminum cation(Al³⁺) or any combination thereof. In some embodiments, the boron (B)oxide is a lithium tetraborate salt (Li₂B₄O₇) (and see also borate salts102A). Non limiting examples of zirconium complexes include zirconiumcomplex of tetra-2-hydroxypropyl ethylenediamine and ammonium zirconiumcarbonate. Non limiting examples of tetraalkoxysilane includeteraethoxysilane and tetrapropoxylsilane.

In some embodiments, bonding molecules 116 may comprise salts comprisingcations selected from H⁺, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba, Al³⁺or any combination thereof and anions selected from RCOO⁻, RSO₃ ⁻, RPO₃²⁻, RPO₄ ²⁻ or any combination thereof. In some embodiments, the salt islithium sulfate (Li₂SO₄). In some embodiments, the salt is lithiumphosphate monobasic (H₂LiPO₄). In some embodiments, the salt is lithiumphosphate (Li₃PO₄). In some embodiments, the salt is phosphoric acid(H₃PO₄).

In some embodiments, bonding molecules 116 are represented at least byone of formulas I-VII.

In some embodiments, the invention is directed to a lithium ion cellcomprising a modified graphite anode, represented by the formula Gr-Bz,wherein Gr is graphite anode and Bz is a benzyl moiety. In someembodiments, a benzyl moiety with a good leaving group is reacted withgraphite anode and also with a non-nucleophilic base to form a modifiedgraphite anode, wherein the graphite is attached covalently to the CH₂moiety of the benzylic compound. Non-limiting examples ofnon-nucleophilic bases include 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU),N,N-Diisopropylethylamine (DIPEA) and 2,6-Di-tert-butylpyridine. In someembodiments, the non-nucleophilic base is1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU). In some embodiments thenon-nucleophilic base is N,N-Diisopropylethylamine (DIPEA). In someembodiments the non-nucleophilic base is 2,6-Di-tert-butylpyridine. Insome embodiments the non-nucleophilic base is any combination of theabove referenced non nucleophilic bases. Non limiting examples of goodleaving groups are selected from halides (e.g., Cl, Br, I), mesylate,triflate and tosylate.

In some embodiments, the invention directs to a lithium ion cellcomprising a modified graphite anode, represented by the formula Gr-SR,wherein Gr is graphite anode, SR is a thiolether moiety, wherein R isselected from alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, andbenzyl. In some embodiments, a thiol, RSH, is reacted with graphiteanode and a radical initiator, to form a modified graphite anode,wherein the graphite is attached covalently to the S atom of thethiolether compound. Non-limiting examples of a radical initiatorinclude azo compounds such as azobisisobutyronitrile (AIBN) and1,1′-Azobis(cyclohexanecarbonitrile) (ABCN), organic peroxides such asbenzoyl peroxide and ditertbutylperoxide and inorganic peroxides, e.g.peroxydisulfate. In some embodiments, the radical initiator isazobisisobutyronitrile (AIBN). In some embodiments, the radicalinitiator is 1,1′-Azobis(cyclohexanecarbonitrile) (ABCN). In someembodiments, the radical initiator is benzoyl peroxide. In someembodiments, the radical initiator is ditertbutylperoxide. In someembodiments, the radical initiator is peroxydisulfate. In someembodiments, the radical initiator is any combination of the abovereferenced radical initiators.

In some embodiments, the invention directs to a lithium ion cellcomprising a modified Si anode. In some embodiments, the Si anode isconnected covalently to bonding molecule 116, represented by formulaI-VII. In some embodiments, a Si anode rich in silanol bonds, Si—OH, isreacted with the bonding molecule to afford the modified Si anode. Insome embodiments, a Si anode rich in silanol bonds, Si—OH, is reactedwith Si(OR)₃ moiety in the bonding molecule to afford the modified Sianode. In some embodiments, bonding molecule 116, represented by formulaI-VII, is connected to the Si anode via silanol linkage, Si—O—Si.

In some embodiments, Z is aryl, heterocycloalkyl, crown etheryl,cyclamyl, cyclenyl, cryptandyl, naphthalenyl, anthracenyl,phenanthrenyl, tetracenyl, chrysenyl, triphenylenyl pyrenyl orpentacenyl. In some embodiments, Z is aryl. In some embodiments, Z isheterocycloalkyl. In some embodiments, Z is crown etheryl. In someembodiments, Z is cyclamyl. In some embodiments, Z is cyclenyl. In someembodiments, Z is cryptandyl. In some embodiments, Z is naphthalenyl. Insome embodiments, Z is anthracenyl. In some embodiments, Z isanthracenyl. In some embodiments, Z is phenanthrenyl. In someembodiments, Z is tetracenyl. In some embodiments, Z is chrysenyl. Insome embodiments, Z is triphenylenyl. In some embodiments, Z is pyrenyl.

In some embodiments, Z is pentacenyl.

In some embodiments, L¹ is H, F or R¹⁰¹. In some embodiments, L¹ is H.In some embodiments, L¹ is F. In some embodiments, L¹ is R¹⁰¹.

In some embodiments, L² is H, F or R¹⁰². In some embodiments, L² is H.In some embodiments, L² is F. In some embodiments, L² is R¹⁰².

In some embodiments, L³ is H, F or R¹⁰⁴. In some embodiments, L³ is H.In some embodiments, L³ is F. In some embodiments, L³ is R¹⁰⁴.

In some embodiments, L⁴ is H, F or R¹⁰⁶. In some embodiments, L⁴ is H.In some embodiments, L⁴ is F. In some embodiments, L⁴ is R¹⁰⁶.

In some embodiments, R² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R² is CO₂H. In some embodiments, R² is CO₂M¹. In someembodiments, R² is CO₂R. In some embodiments, R² is SO₃H. In someembodiments, R² is SO₃M¹. In some embodiments, R² is PO₃H². In someembodiments, R² is PO₃M¹ ₂. In some embodiments, R² is PO₃M¹H. In someembodiments, R² is PO₄H₂. In some embodiments, R² is PO₄M¹ ₂. In someembodiments, R² is PO₄M¹H. In some embodiments, R² is PO₄M². In someembodiments, R² is C(O)NHOH. In some embodiments, R² is NH₂. In someembodiments, R² is NHR. In some embodiments, R² is N(R)₂. In someembodiments, R² is NO₂. In some embodiments, R² is COOR. In someembodiments, R² is CHO. In some embodiments, R² is CH₂OH. In someembodiments, R² is OH. In some embodiments, R² is OR. In someembodiments, R³ is SH. In some embodiments, R² is SR. In someembodiments, R² is C(O)N(R)₂. In some embodiments, R² is C(O)NHR. Insome embodiments, R² is C(O)NH₂. In some embodiments, R² is halide. Insome embodiments, R² is tosylate. In some embodiments, R² is mesylate.In some embodiments, R² is SO₂NHR. In some embodiments, R² is triflate.In some embodiments, R² is isocyanate. In some embodiments, R² iscyanate. In some embodiments, R² is thiocyanate. In some embodiments, R²is isothiocyanate. In some embodiments, R² is R. In some embodiments, R²is cyano. In some embodiments, R² is CF₃. In some embodiments, R² isSi(OR)₃.

In some embodiments, R³ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R³ is CO₂H. In some embodiments, R³ is CO₂M¹. In someembodiments, R³ is CO₂R. In some embodiments, R³ is SO₃H. In someembodiments, R³ is SO₃M¹. In some embodiments, R³ is PO₃H². In someembodiments, R³ is PO₃M¹ ₂. In some embodiments, R³ is PO₃M¹H. In someembodiments, R³ is PO₄H₂. In some embodiments, R³ is PO₄M¹ ₂. In someembodiments, R³ is PO₄M¹H. In some embodiments, R³ is PO₄M². In someembodiments, R³ is C(O)NHOH. In some embodiments, R³ is NH₂. In someembodiments, R³ is NHR. In some embodiments, R³ is N(R)₂. In someembodiments, R³ is NO₂. In some embodiments, R³ is COOR. In someembodiments, R³ is CHO. In some embodiments, R³ is CH₂OH. In someembodiments, R³ is OH. In some embodiments, R³ is OR. In someembodiments, R³ is SH. In some embodiments, R³ is SR. In someembodiments, R³ is C(O)N(R)₂. In some embodiments, R³ is C(O)NHR. Insome embodiments, R³ is C(O)NH₂. In some embodiments, R³ is halide. Insome embodiments, R³ is tosylate. In some embodiments, R³ is mesylate.In some embodiments, R³ is SO₂NHR. In some embodiments, R³ is triflate.In some embodiments, R³ is isocyanate. In some embodiments, R³ iscyanate. In some embodiments, R³ is thiocyanate. In some embodiments, R³is isothiocyanate. In some embodiments, R³ is R. In some embodiments, R³is cyano. In some embodiments, R³ is CF₃. In some embodiments, R³ isSi(OR)₃.

In some embodiments, R⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R⁴ is CO₂H. In some embodiments, R⁴ is CO₂M¹. In someembodiments, R⁴ is CO₂R. In some embodiments, R⁴ is SO₃H. In someembodiments, R⁴ is SO₃M¹. In some embodiments, R⁴ is PO₃H². In someembodiments, R⁴ is PO₃M¹ ₂. In some embodiments, R⁴ is PO₃M¹H. In someembodiments, R⁴ is PO₄H₂. In some embodiments, R⁴ is PO₄M¹ ₂. In someembodiments, R⁴ is PO₄M¹H. In some embodiments, R⁴ is PO₄M². In someembodiments, R⁴ is C(O)NHOH. In some embodiments, R⁴ is NH₂. In someembodiments, R⁴ is NHR. In some embodiments, R⁴ is N(R)₂. In someembodiments, R⁴ is NO₂. In some embodiments, R⁴ is COOR. In someembodiments, R⁴ is CHO. In some embodiments, R⁴ is CH₂OH. In someembodiments, R⁴ is OH. In some embodiments, R⁴ is OR. In someembodiments, R⁴ is SH. In some embodiments, R⁴ is SR. In someembodiments, R⁴ is C(O)N(R)₂. In some embodiments, R⁴ is C(O)NHR. Insome embodiments, R⁴ is C(O)NH₂. In some embodiments, R⁴ is halide. Insome embodiments, R⁴ is tosylate. In some embodiments, R⁴ is mesylate.In some embodiments, R⁴ is SO₂NHR. In some embodiments, R⁴ is triflate.In some embodiments, R⁴ is isocyanate. In some embodiments, R⁴ iscyanate. In some embodiments, R⁴ is thiocyanate. In some embodiments, R⁴is isothiocyanate. In some embodiments, R⁴ is R. In some embodiments, R⁴is cyano. In some embodiments, R⁴ is CF₃. In some embodiments, R⁴ isSi(OR)₃.

In some embodiments, R⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R⁵ is CO₂H. In some embodiments, R⁵ is CO₂M¹. In someembodiments, R⁵ is CO₂R. In some embodiments, R⁵ is SO₃H. In someembodiments, R⁵ is SO₃M¹. In some embodiments, R⁵ is PO₃H². In someembodiments, R⁵ is PO₃M¹ ₂. In some embodiments, R⁵ is PO₃M¹H. In someembodiments, R⁵ is PO₄H₂. In some embodiments, R⁵ is PO₄M¹ ₂. In someembodiments, R⁵ is PO₄M¹H. In some embodiments, R⁵ is PO₄M². In someembodiments, R⁵ is C(O)NHOH. In some embodiments, R⁵ is NH₂. In someembodiments, R⁵ is NHR. In some embodiments, R⁵ is N(R)₂. In someembodiments, R⁵ is NO₂. In some embodiments, R⁵ is COOR. In someembodiments, R⁵ is CHO. In some embodiments, R⁵ is CH₂OH. In someembodiments, R⁵ is OH. In some embodiments, R⁵ is OR. In someembodiments, R⁵ is SH. In some embodiments, R⁵ is SR. In someembodiments, R⁵ is C(O)N(R)₂. In some embodiments, R⁵ is C(O)NHR. Insome embodiments, R⁵ is C(O)NH₂. In some embodiments, R⁵ is halide. Insome embodiments, R⁵ is tosylate. In some embodiments, R⁵ is mesylate.In some embodiments, R⁵ is SO₂NHR. In some embodiments, R⁵ is triflate.In some embodiments, R⁵ is isocyanate. In some embodiments, R⁵ iscyanate. In some embodiments, R⁵ is thiocyanate. In some embodiments, R⁵is isothiocyanate. In some embodiments, R⁵ is R. In some embodiments, R⁵is cyano. In some embodiments, R⁵ is CF₃. In some embodiments, R⁵ isSi(OR)₃.

In some embodiments, R⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R⁶ is CO₂H. In some embodiments, R⁶ is CO₂M¹. In someembodiments, R⁶ is CO₂R. In some embodiments, R⁶ is SO₃H. In someembodiments, R⁶ is SO₃M¹. In some embodiments, R⁶ is PO₃H². In someembodiments, R⁶ is PO₃M¹ ₂. In some embodiments, R⁶ is PO₃M¹H. In someembodiments, R⁶ is PO₄H₂. In some embodiments, R⁶ is PO₄M¹ ₂. In someembodiments, R⁶ is PO₄M¹H. In some embodiments, R⁶ is PO₄M². In someembodiments, R⁶ is C(O)NHOH. In some embodiments, R⁶ is NH₂. In someembodiments, R⁶ is NHR. In some embodiments, R⁶ is N(R)₂. In someembodiments, R⁶ is NO₂. In some embodiments, R⁶ is COOR. In someembodiments, R⁶ is CHO. In some embodiments, R⁶ is CH₂OH. In someembodiments, R⁶ is OH. In some embodiments, R⁶ is OR. In someembodiments, R⁶ is SH. In some embodiments, R⁶ is SR. In someembodiments, R⁵ is C(O)N(R)₂. In some embodiments, R⁵ is C(O)NHR. Insome embodiments, R⁵ is C(O)NH₂. In some embodiments, R⁶ is halide. Insome embodiments, R⁶ is tosylate. In some embodiments, R⁶ is mesylate.In some embodiments, R⁶ is SO₂NHR. In some embodiments, R⁶ is triflate.In some embodiments, R⁶ is isocyanate. In some embodiments, R⁶ iscyanate. In some embodiments, R⁶ is thiocyanate. In some embodiments, R⁶is isothiocyanate. In some embodiments, R⁶ is R. In some embodiments, R⁶is cyano. In some embodiments, R⁶ is CF₃. In some embodiments, R⁶ isSi(OR)₃.

In some embodiments, R⁸ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R⁸ is CO₂H. In some embodiments, R⁸ is CO₂M¹. In someembodiments, R⁸ is CO₂R. In some embodiments, R⁸ is SO₃H. In someembodiments, R⁸ is SO₃M¹. In some embodiments, R⁸ is PO₃H². In someembodiments, R⁸ is PO₃M¹ ₂. In some embodiments, R⁵ is PO₃M¹H. In someembodiments, R⁸ is PO₄H₂. In some embodiments, R⁸ is PO₄M¹ ₂. In someembodiments, R⁸ is PO₄M¹H. In some embodiments, R⁸ is PO₄M². In someembodiments, R⁸ is C(O)NHOH. In some embodiments, R⁸ is NH₂. In someembodiments, R⁸ is NHR. In some embodiments, R⁸ is N(R)₂. In someembodiments, R⁸ is NO₂. In some embodiments, R⁸ is COOR. In someembodiments, R⁸ is CHO. In some embodiments, R⁸ is CH₂OH. In someembodiments, R⁸ is OH. In some embodiments, R⁸ is OR. In someembodiments, R⁸ is SH. In some embodiments, R⁸ is SR. In someembodiments, R⁸ is C(O)N(R)₂. In some embodiments, R⁸ is C(O)NHR. Insome embodiments, R⁸ is C(O)NH₂. In some embodiments, R⁸ is halide. Insome embodiments, R⁸ is tosylate. In some embodiments, R⁸ is mesylate.In some embodiments, R⁸ is SO₂NHR. In some embodiments, R⁸ is triflate.In some embodiments, R⁸ is isocyanate. In some embodiments, R⁸ iscyanate. In some embodiments, R⁸ is thiocyanate. In some embodiments, R⁸is isothiocyanate. In some embodiments, R⁸ is R. In some embodiments, R⁸is cyano. In some embodiments, R⁸ is CF₃. In some embodiments, R⁸ isSi(OR)₃.

In some embodiments, R⁹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano, CF₃ or Si(OR)₃. In someembodiments, R⁹ is CO₂H. In some embodiments, R⁹ is CO₂M¹. In someembodiments, R⁹ is CO₂R. In some embodiments, R⁹ is SO₃H. In someembodiments, R⁹ is SO₃M¹. In some embodiments, R⁹ is PO₃H². In someembodiments, R⁹ is PO₃M¹ ₂. In some embodiments, R⁹ is PO₃M¹H. In someembodiments, R⁹ is PO₄H₂. In some embodiments, R⁹ is PO₄M¹ ₂. In someembodiments, R⁹ is PO₄M¹H. In some embodiments, R⁹ is PO₄M². In someembodiments, R⁹ is C(O)NHOH. In some embodiments, R⁹ is NH₂. In someembodiments, R⁹ is NHR. In some embodiments, R⁹ is N(R)₂. In someembodiments, R⁹ is NO₂. In some embodiments, R⁹ is COOR. In someembodiments, R⁹ is CHO. In some embodiments, R⁹ is CH₂OH. In someembodiments, R⁹ is OH. In some embodiments, R⁹ is OR. In someembodiments, R⁵ is SH. In some embodiments, R⁹ is SR. In someembodiments, R⁹ is C(O)N(R)₂. In some embodiments, R⁹ is C(O)NHR. Insome embodiments, R⁹ is C(O)NH₂. In some embodiments, R⁹ is halide. Insome embodiments, R⁹ is tosylate. In some embodiments, R⁹ is mesylate.In some embodiments, R⁹ is SO₂NHR. In some embodiments, R⁹ is triflate.In some embodiments, R⁹ is isocyanate. In some embodiments, R⁹ iscyanate. In some embodiments, R⁹ is thiocyanate. In some embodiments, R⁹is isothiocyanate. In some embodiments, R⁹ is R. In some embodiments, R⁹is cyano. In some embodiments, R⁹ is CF₃. In some embodiments, R⁹ isSi(OR)₃.

In some embodiments, R¹⁰ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰ is CO₂H. In some embodiments, R¹⁰ is CO₂M¹. In someembodiments, R¹⁰ is CO₂R. In some embodiments, R¹⁰ is SO₃H. In someembodiments, R¹⁰ is SO₃M¹. In some embodiments, R¹⁰ is PO₃H². In someembodiments, R¹⁰ is PO₃M¹ ₂. In some embodiments, R¹⁰ is PO₃M¹H. In someembodiments, R¹⁰ is PO₄H₂. In some embodiments, R¹⁰ is PO₄M¹ ₂. In someembodiments, R¹⁰ is PO₄M¹H. In some embodiments, R¹⁰ is PO₄M². In someembodiments, R¹⁰ is C(O)NHOH. In some embodiments, R¹⁰ is NH₂. In someembodiments, R¹⁰ is NHR. In some embodiments, R¹⁰ is N(R)₂. In someembodiments, R¹⁰ is NO₂. In some embodiments, R¹⁰ is COOR. In someembodiments, R¹⁰ is CHO. In some embodiments, R¹⁰ is CH₂OH. In someembodiments, R¹⁰ is OH. In some embodiments, R¹⁰ is OR. In someembodiments, R¹⁰ is SH. In some embodiments, R¹⁰ is SR. In someembodiments, R¹⁰ is C(O)N(R)₂. In some embodiments, R¹⁰ is C(O)NHR. Insome embodiments, R¹⁰ is C(O)NH₂. In some embodiments, R¹⁰ is halide. Insome embodiments, R¹⁰ is tosylate. In some embodiments, R¹⁰ is mesylate.In some embodiments, R¹⁰ is SO₂NHR. In some embodiments, R¹⁰ istriflate. In some embodiments, R¹⁰ is isocyanate. In some embodiments,R¹⁰ is cyanate. In some embodiments, R¹⁰ is thiocyanate. In someembodiments, R¹⁰ is isothiocyanate. In some embodiments, R¹⁰ is R. Insome embodiments, R¹⁰ is cyano. In some embodiments, R¹⁰ is CF₃. In someembodiments, R¹⁰ is Si(OR)₃.

In some embodiments, R¹¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹¹ is CO₂H. In some embodiments, R¹¹ is CO₂M¹. In someembodiments, R¹¹ is CO₂R. In some embodiments, R¹¹ is SO₃H. In someembodiments, R¹¹ is SO₃M¹. In some embodiments, R¹¹ is PO₃H². In someembodiments, R¹¹ is PO₃M¹ ₂. In some embodiments, R¹¹ is PO₃M¹H. In someembodiments, R¹¹ is PO₄H₂. In some embodiments, R¹¹ is PO₄M¹ ₂. In someembodiments, R¹¹ is PO₄M¹H. In some embodiments, R¹¹ is PO₄M². In someembodiments, R¹¹ is C(O)NHOH. In some embodiments, R¹¹ is NH₂. In someembodiments, R¹¹ is NHR. In some embodiments, R¹¹ is N(R)₂. In someembodiments, R¹¹ is NO₂. In some embodiments, R¹¹ is COOR. In someembodiments, R¹¹ is CHO. In some embodiments, R¹¹ is CH₂OH. In someembodiments, R¹¹ is OH. In some embodiments, R¹¹ is OR. In someembodiments, R¹¹ is SH. In some embodiments, R¹¹ is SR. In someembodiments, R¹¹ is C(O)N(R)₂. In some embodiments, R¹¹ is C(O)NHR. Insome embodiments, R¹¹ is C(O)NH₂. In some embodiments, R¹¹ is halide. Insome embodiments, R¹¹ is tosylate. In some embodiments, R¹¹ is mesylate.In some embodiments, R¹¹ is SO₂NHR. In some embodiments, R¹¹ istriflate. In some embodiments, R¹¹ is isocyanate. In some embodiments,R¹¹ is cyanate. In some embodiments, R¹¹ is thiocyanate. In someembodiments, R¹¹ is isothiocyanate. In some embodiments, R¹¹ is R. Insome embodiments, R¹¹ is cyano. In some embodiments, R¹¹ is CF₃. In someembodiments, R¹¹ is Si(OR)₃.

In some embodiments, R¹² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹² is CO₂H. In some embodiments, R¹² is CO₂M¹. In someembodiments, R¹² is CO₂R. In some embodiments, R¹² is SO₃H. In someembodiments, R¹² is SO₃M¹. In some embodiments, R¹² is PO₃H². In someembodiments, R¹² is PO₃M¹ ₂. In some embodiments, R¹² is PO₃M¹H. In someembodiments, R¹² is PO₄H₂. In some embodiments, R¹² is PO₄M¹ ₂. In someembodiments, R¹² is PO₄M¹H. In some embodiments, R¹² is PO₄M². In someembodiments, R¹² is C(O)NHOH. In some embodiments, R¹² is NH₂. In someembodiments, R¹² is NHR. In some embodiments, R¹² is N(R)₂. In someembodiments, R¹² is NO₂. In some embodiments, R¹² is COOR. In someembodiments, R¹² is CHO. In some embodiments, R¹² is CH₂OH. In someembodiments, R¹² is OH. In some embodiments, R¹² is OR. In someembodiments, R¹² is SH. In some embodiments, R¹² is SR. In someembodiments, R¹² is C(O)N(R)₂. In some embodiments, R¹² is C(O)NHR. Insome embodiments, R¹² is C(O)NH₂. In some embodiments, R¹² is halide. Insome embodiments, R¹² is tosylate. In some embodiments, R¹² is mesylate.In some embodiments, R¹² is SO₂NHR. In some embodiments, R¹² istriflate. In some embodiments, R¹² is isocyanate. In some embodiments,R¹² is cyanate. In some embodiments, R¹² is thiocyanate. In someembodiments, R¹² is isothiocyanate. In some embodiments, R¹² is R. Insome embodiments, R¹² is cyano. In some embodiments, R¹² is CF₃. In someembodiments, R⁵ is Si(OR)₃.

In some embodiments, R¹³ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹³ is CO₂H. In some embodiments, R¹³ is CO₂M¹. In someembodiments, R¹³ is CO₂R. In some embodiments, R¹³ is SO₃H. In someembodiments, R¹³ is SO₃M¹. In some embodiments, R¹³ is PO₃H². In someembodiments, R¹³ is PO₃M¹ ₂. In some embodiments, R¹³ is PO₃M¹H. In someembodiments, R¹³ is PO₄H₂. In some embodiments, R¹³ is PO₄M¹ ₂. In someembodiments, R¹³ is PO₄M¹H. In some embodiments, R¹³ is PO₄M². In someembodiments, R¹³ is C(O)NHOH. In some embodiments, R¹³ is NH₂. In someembodiments, R¹³ is NHR. In some embodiments, R¹³ is N(R)₂. In someembodiments, R¹³ is NO₂. In some embodiments, R¹³ is COOR. In someembodiments, R¹³ is CHO. In some embodiments, R¹³ is CH₂OH. In someembodiments, R¹³ is OH. In some embodiments, R¹³ is OR. In someembodiments, R¹³ is SH. In some embodiments, R⁵ is SR. In someembodiments, R¹³ is C(O)N(R)₂. In some embodiments, R¹³ is C(O)NHR. Insome embodiments, R¹³ is C(O)NH₂. In some embodiments, R¹³ is halide. Insome embodiments, R¹³ is tosylate. In some embodiments, R¹³ is mesylate.In some embodiments, R¹³ is SO₂NHR. In some embodiments, R¹³ istriflate. In some embodiments, R¹³ is isocyanate. In some embodiments,R¹³ is cyanate. In some embodiments, R¹³ is thiocyanate. In someembodiments, R¹³ is isothiocyanate. In some embodiments, R¹³ is R. Insome embodiments, R¹³ is cyano. In some embodiments, R¹³ is CF₃. In someembodiments, R¹³ is Si(OR)₃.

In some embodiments, R¹⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁴ is CO₂H. In some embodiments, R¹⁴ is CO₂M¹. In someembodiments, R¹⁴ is CO₂R. In some embodiments, R¹⁴ is SO₃H. In someembodiments, R¹⁴ is SO₃M¹. In some embodiments, R¹⁴ is PO₃H². In someembodiments, R¹⁴ is PO₃M¹ ₂. In some embodiments, R¹⁴ is PO₃M¹H. In someembodiments, R¹⁴ is PO₄H₂. In some embodiments, R¹⁴ is PO₄M¹ ₂. In someembodiments, R¹⁴ is PO₄M¹H. In some embodiments, R¹⁴ is PO₄M². In someembodiments, R¹⁴ is C(O)NHOH. In some embodiments, R¹⁴ is NH₂. In someembodiments, R¹⁴ is NHR. In some embodiments, R¹⁴ is N(R)₂. In someembodiments, R¹⁴ is NO₂. In some embodiments, R¹⁴ is COOR. In someembodiments, R¹⁴ is CHO. In some embodiments, R¹⁴ is CH₂OH. In someembodiments, R¹⁴ is OH. In some embodiments, R¹⁴ is OR. In someembodiments, R¹⁴ is SH. In some embodiments, R¹⁴ is SR. In someembodiments, R¹⁴ is C(O)N(R)₂. In some embodiments, R¹⁴ is C(O)NHR. Insome embodiments, R¹⁴ is C(O)NH₂. In some embodiments, R¹⁴ is halide. Insome embodiments, R¹⁴ is tosylate. In some embodiments, R¹⁴ is mesylate.In some embodiments, R¹⁴ is SO₂NHR. In some embodiments, R¹⁴ istriflate. In some embodiments, R¹⁴ is isocyanate. In some embodiments,R¹⁴ is cyanate. In some embodiments, R¹⁴ is thiocyanate. In someembodiments, R¹⁴ is isothiocyanate. In some embodiments, R¹⁴ is R. Insome embodiments, R¹⁴ is cyano. In some embodiments, R¹⁴ is CF₃. In someembodiments, R¹⁴ is Si(OR)₃.

In some embodiments, R¹⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁵ is CO₂H. In some embodiments, R¹⁵ is CO₂M¹. In someembodiments, R¹⁵ is CO₂R. In some embodiments, R¹⁵ is SO₃H. In someembodiments, R¹⁵ is SO₃M¹. In some embodiments, R¹⁵ is PO₃H². In someembodiments, R¹⁵ is PO₃M¹ ₂. In some embodiments, R¹⁵ is PO₃M¹H. In someembodiments, R¹⁵ is PO₄H₂. In some embodiments, R¹⁵ is PO₄M¹ ₂. In someembodiments, R¹⁵ is PO₄M¹H. In some embodiments, R¹⁵ is PO₄M². In someembodiments, R¹⁵ is C(O)NHOH. In some embodiments, R¹⁵ is NH₂. In someembodiments, R¹⁵ is NHR. In some embodiments, R¹⁵ is N(R)₂. In someembodiments, R¹⁵ is NO₂. In some embodiments, R¹⁵ is COOR. In someembodiments, R¹⁵ is CHO. In some embodiments, R¹⁵ is CH₂OH. In someembodiments, R¹⁵ is OH. In some embodiments, R¹⁵ is OR. In someembodiments, R¹⁵ is SH. In some embodiments, R¹⁵ is SR. In someembodiments, R¹⁵ is C(O)N(R)₂. In some embodiments, R¹⁵ is C(O)NHR. Insome embodiments, R¹⁵ is C(O)NH₂. In some embodiments, R¹⁵ is halide. Insome embodiments, R¹⁵ is tosylate. In some embodiments, R¹⁵ is mesylate.In some embodiments, R¹⁵ is SO₂NHR. In some embodiments, R¹⁵ istriflate. In some embodiments, R¹⁵ is isocyanate. In some embodiments,R¹⁵ is cyanate. In some embodiments, R¹⁵ is thiocyanate. In someembodiments, R¹⁵ is isothiocyanate. In some embodiments, R¹⁵ is R. Insome embodiments, R¹⁵ is cyano. In some embodiments, R¹⁵ is CF₃. In someembodiments, R¹⁵ is Si(OR)₃.

In some embodiments, R¹⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁶ is CO₂H. In some embodiments, R¹⁶ is CO₂M¹. In someembodiments, R¹⁶ is CO₂R. In some embodiments, R¹⁶ is SO₃H. In someembodiments, R¹⁶ is SO₃M¹. In some embodiments, R¹⁶ is PO₃H². In someembodiments, R¹⁶ is PO₃M¹ ₂. In some embodiments, R¹⁶ is PO₃M¹H. In someembodiments, R¹⁶ is PO₄H₂. In some embodiments, R¹⁶ is PO₄M¹ ₂. In someembodiments, R¹⁶ is PO₄M¹H. In some embodiments, R¹⁶ is PO₄M². In someembodiments, R¹⁶ is C(O)NHOH. In some embodiments, R¹⁶ is NH₂. In someembodiments, R¹⁶ is NHR. In some embodiments, R¹⁶ is N(R)₂. In someembodiments, R¹⁶ is NO₂. In some embodiments, R¹⁶ is COOR. In someembodiments, R¹⁶ is CHO. In some embodiments, R¹⁶ is CH₂OH. In someembodiments, R¹⁶ is OH. In some embodiments, R¹⁶ is OR. In someembodiments, R¹⁶ is SH. In some embodiments, R¹⁶ is SR. In someembodiments, R¹⁶ is C(O)N(R)₂. In some embodiments, R¹⁶ is C(O)NHR. Insome embodiments, R¹⁶ is C(O)NH₂. In some embodiments, R¹⁶ is halide. Insome embodiments, R¹⁶ is tosylate. In some embodiments, R¹⁶ is mesylate.In some embodiments, R¹⁶ is SO₂NHR. In some embodiments, R¹⁶ istriflate. In some embodiments, R¹⁶ is isocyanate. In some embodiments,R¹⁶ is cyanate. In some embodiments, R¹⁶ is thiocyanate. In someembodiments, R¹⁶ is isothiocyanate. In some embodiments, R¹⁶ is R. Insome embodiments, R¹⁶ is cyano. In some embodiments, R¹⁶ is CF₃. In someembodiments, R¹⁶ is Si(OR)₃.

In some embodiments, R¹⁷ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁷ is CO₂H. In some embodiments, R¹⁷ is CO₂M¹. In someembodiments, R¹⁷ is CO₂R. In some embodiments, R¹⁷ is SO₃H. In someembodiments, R¹⁷ is SO₃M¹. In some embodiments, R¹⁷ is PO₃H². In someembodiments, R¹⁷ is PO₃M¹ ₂. In some embodiments, R¹⁷ is PO₃M¹H. In someembodiments, R¹⁷ is PO₄H₂. In some embodiments, R¹⁷ is PO₄M¹ ₂. In someembodiments, R¹⁷ is PO₄M¹H. In some embodiments, R¹⁷ is PO₄M². In someembodiments, R¹⁷ is C(O)NHOH. In some embodiments, R¹⁷ is NH₂. In someembodiments, R¹⁷ is NHR. In some embodiments, R¹⁷ is N(R)₂. In someembodiments, R¹⁷ is NO₂. In some embodiments, R¹⁷ is COOR. In someembodiments, R¹⁷ is CHO. In some embodiments, R¹⁷ is CH₂OH. In someembodiments, R¹⁷ is OH. In some embodiments, R¹⁷ is OR. In someembodiments, R¹⁷ is SH. In some embodiments, R¹⁷ is SR. In someembodiments, R¹⁷ is C(O)N(R)₂. In some embodiments, R¹⁷ is C(O)NHR. Insome embodiments, R¹⁷ is C(O)NH₂. In some embodiments, R¹⁷ is halide. Insome embodiments, R¹⁷ is tosylate. In some embodiments, R¹⁷ is mesylate.In some embodiments, R¹⁷ is SO₂NHR. In some embodiments, R¹⁷ istriflate. In some embodiments, R¹⁷ is isocyanate. In some embodiments,R¹⁷ is cyanate. In some embodiments, R¹⁷ is thiocyanate. In someembodiments, R¹⁷ is isothiocyanate. In some embodiments, R¹⁷ is R. Insome embodiments, R¹⁷ is cyano. In some embodiments, R¹⁷ is CF₃. In someembodiments, R¹⁷ is Si(OR)₃.

In some embodiments, R¹⁸ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁸ is CO₂H. In some embodiments, R¹⁸ is CO₂M¹. In someembodiments, R¹⁸ is CO₂R. In some embodiments, R¹⁸ is SO₃H. In someembodiments, R¹⁸ is SO₃M¹. In some embodiments, R¹⁸ is PO₃H². In someembodiments, R¹⁸ is PO₃M¹ ₂. In some embodiments, R¹⁸ is PO₃M¹H. In someembodiments, R¹⁸ is PO₄H₂. In some embodiments, R¹⁸ is PO₄M¹ ₂. In someembodiments, R¹⁸ is PO₄M¹H. In some embodiments, R¹⁸ is PO₄M². In someembodiments, R¹⁸ is C(O)NHOH. In some embodiments, R¹⁸ is NH₂. In someembodiments, R¹⁸ is NHR. In some embodiments, R¹⁸ is N(R)₂. In someembodiments, R¹⁸ is NO₂. In some embodiments, R¹⁸ is COOR. In someembodiments, R¹⁸ is CHO. In some embodiments, R¹⁸ is CH₂OH. In someembodiments, R¹⁸ is OH. In some embodiments, R¹⁸ is OR. In someembodiments, R¹³ is SH. In some embodiments, R¹⁸ is SR. In someembodiments, R¹⁸ is C(O)N(R)₂. In some embodiments, R¹⁸ is C(O)NHR. Insome embodiments, R¹⁸ is C(O)NH₂. In some embodiments, R¹⁸ is halide. Insome embodiments, R¹⁸ is tosylate. In some embodiments, R¹⁸ is mesylate.In some embodiments, R¹⁸ is SO₂NHR. In some embodiments, R¹⁸ istriflate. In some embodiments, R¹⁸ is isocyanate. In some embodiments,R¹⁸ is cyanate. In some embodiments, R¹⁸ is thiocyanate. In someembodiments, R¹⁸ is isothiocyanate. In some embodiments, R¹⁸ is R. Insome embodiments, R¹⁸ is cyano. In some embodiments, R¹⁸ is CF₃. In someembodiments, R¹³ is Si(OR)₃.

In some embodiments, R¹⁹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁹ is CO₂H. In some embodiments, R¹⁹ is CO₂M¹. In someembodiments, R¹⁹ is CO₂R. In some embodiments, R¹⁹ is SO₃H. In someembodiments, R¹⁹ is SO₃M¹. In some embodiments, R¹⁹ is PO₃H². In someembodiments, R¹⁹ is PO₃M¹ ₂. In some embodiments, R¹⁹ is PO₃M¹H. In someembodiments, R¹⁹ is PO₄H₂. In some embodiments, R¹⁹ is PO₄M¹ ₂. In someembodiments, R¹⁹ is PO₄M¹H. In some embodiments, R¹⁹ is PO₄M². In someembodiments, R¹⁹ is C(O)NHOH. In some embodiments, R¹⁹ is NH₂. In someembodiments, R¹⁹ is NHR. In some embodiments, R¹⁹ is N(R)₂. In someembodiments, R¹⁹ is NO₂. In some embodiments, R¹⁹ is COOR. In someembodiments, R¹⁹ is CHO. In some embodiments, R¹⁹ is CH₂OH. In someembodiments, R¹⁹ is OH. In some embodiments, R¹⁹ is OR. In someembodiments, R¹⁹ is SH. In some embodiments, R¹⁹ is SR. In someembodiments, R¹⁹ is C(O)N(R)₂. In some embodiments, R¹⁹ is C(O)NHR. Insome embodiments, R¹⁹ is C(O)NH₂. In some embodiments, R¹⁹ is halide. Insome embodiments, R¹⁹ is tosylate. In some embodiments, R¹⁹ is mesylate.In some embodiments, R¹⁹ is SO₂NHR. In some embodiments, R¹⁹ istriflate. In some embodiments, R¹⁹ is isocyanate. In some embodiments,R¹⁹ is cyanate. In some embodiments, R¹⁹ is thiocyanate. In someembodiments, R¹⁹ is isothiocyanate. In some embodiments, R¹⁹ is R. Insome embodiments, R¹⁹ is cyano. In some embodiments, R¹⁹ is CF₃. In someembodiments, R¹⁹ is Si(OR)₃.

In some embodiments, R²⁰ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R²⁰ is CO₂H. In some embodiments, R²⁰ is CO₂M¹. In someembodiments, R²⁰ is CO₂R. In some embodiments, R²⁰ is SO₃H. In someembodiments, R²⁰ is SO₃M¹. In some embodiments, R²⁰ is PO₃H². In someembodiments, R²⁰ is PO₃M¹ ₂. In some embodiments, R²⁰ is PO₃M¹H. In someembodiments, R²⁰ is PO₄H₂. In some embodiments, R²⁰ is PO₄M¹ ₂. In someembodiments, R²⁰ is PO₄M¹H. In some embodiments, R²⁰ is PO₄M². In someembodiments, R²⁰ is C(O)NHOH. In some embodiments, R²⁰ is NH₂. In someembodiments, R²⁰ is NHR. In some embodiments, R²⁰ is N(R)₂. In someembodiments, R²⁰ is NO₂. In some embodiments, R²⁰ is COOR. In someembodiments, R²⁰ is CHO. In some embodiments, R²⁰ is CH₂OH. In someembodiments, R²⁰ is OH. In some embodiments, R²⁰ is OR. In someembodiments, R¹³ is SH. In some embodiments, R²⁰ is SR. In someembodiments, R²⁰ is C(O)N(R)₂. In some embodiments, R²⁰ is C(O)NHR. Insome embodiments, R²⁰ is C(O)NH₂. In some embodiments, R²⁰ is halide. Insome embodiments, R²⁰ is tosylate. In some embodiments, R²⁰ is mesylate.In some embodiments, R²⁰ is SO₂NHR. In some embodiments, R²⁰ istriflate. In some embodiments, R²⁰ is isocyanate. In some embodiments,R²⁰ is cyanate. In some embodiments, R²⁰ is thiocyanate. In someembodiments, R²⁰ is isothiocyanate. In some embodiments, R²⁰ is R. Insome embodiments, R²⁰ is cyano. In some embodiments, R²⁰ is CF₃. In someembodiments, R²⁰ is Si(OR)₃.

In some embodiments, R²¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R²¹ is CO₂H. In some embodiments, R²¹ is CO₂M¹. In someembodiments, R²¹ is CO₂R. In some embodiments, R²¹ is SO₃H. In someembodiments, R²¹ is SO₃M¹. In some embodiments, R²¹ is PO₃H². In someembodiments, R²¹ is PO₃M¹ ₂. In some embodiments, R²¹ is PO₃M¹H. In someembodiments, R²¹ is PO₄H₂. In some embodiments, R²¹ is PO₄M¹ ₂. In someembodiments, R²¹ is PO₄M¹H. In some embodiments, R²¹ is PO₄M². In someembodiments, R²¹ is C(O)NHOH. In some embodiments, R²¹ is NH₂. In someembodiments, R²¹ is NHR. In some embodiments, R²¹ is N(R)₂. In someembodiments, R²¹ is NO₂. In some embodiments, R²¹ is COOR. In someembodiments, R²¹ is CHO. In some embodiments, R²¹ is CH₂OH. In someembodiments, R²¹ is OH. In some embodiments, R²¹ is OR. In someembodiments, R¹³ is SH. In some embodiments, R²¹ is SR. In someembodiments, R²¹ is C(O)N(R)₂. In some embodiments, R²¹ is C(O)NHR. Insome embodiments, R²¹ is C(O)NH₂. In some embodiments, R²¹ is halide. Insome embodiments, R²¹ is tosylate. In some embodiments, R²¹ is mesylate.In some embodiments, R²¹ is SO₂NHR. In some embodiments, R²¹ istriflate. In some embodiments, R²¹ is isocyanate. In some embodiments,R²¹ is cyanate. In some embodiments, R²¹ is thiocyanate. In someembodiments, R²¹ is isothiocyanate. In some embodiments, R²¹ is R. Insome embodiments, R²¹ is cyano. In some embodiments, R²¹ is CF₃. In someembodiments, R²¹ is Si(OR)₃.

In some embodiments, R²² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H², PO₃M¹₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂,NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂,halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R²² is CO₂H. In some embodiments, R²² is CO₂M¹. In someembodiments, R²² is CO₂R. In some embodiments, R²² is SO₃H. In someembodiments, R²² is SO₃M¹. In some embodiments, R²² is PO₃H². In someembodiments, R²² is PO₃M¹ ₂. In some embodiments, R²² is PO₃M¹H. In someembodiments, R²² is PO₄H₂.

In some embodiments, R²² is PO₄M¹ ₂. In some embodiments, R²² is PO₄M¹H.In some embodiments, R²² is PO₄M². In some embodiments, R²² is C(O)NHOH.In some embodiments, R²² is NH₂. In some embodiments, R²² is NHR. Insome embodiments, R²² is N(R)₂. In some embodiments, R²² is NO₂. In someembodiments, R²² is COOR. In some embodiments, R²² is CHO. In someembodiments, R²² is CH₂OH. In some embodiments, R²² is OH. In someembodiments, R²² is OR. In some embodiments, R²² is SH. In someembodiments, R²² is SR. In some embodiments, R²² is C(O)N(R)₂. In someembodiments, R²² is C(O)NHR. In some embodiments, R²² is C(O)NH₂. Insome embodiments, R²² is halide. In some embodiments, R²² is tosylate.In some embodiments, R²² is mesylate. In some embodiments, R²² isSO₂NHR. In some embodiments, R²² is triflate. In some embodiments, R²²is isocyanate. In some embodiments, R²² is cyanate. In some embodiments,R²² is thiocyanate. In some embodiments, R²² is isothiocyanate. In someembodiments, R²² is R. In some embodiments, R²² is cyano. In someembodiments, R²² is CF₃. In some embodiments, R²² is Si(OR)₃.

In some embodiments, R¹⁰¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰¹ is CO₂H. In some embodiments, R¹⁰¹ is CO₂M¹. In someembodiments, R¹⁰¹ is CO₂R. In some embodiments, R¹⁰¹ is SO₃H. In someembodiments, R¹⁰¹ is SO₃M¹. In some embodiments, R¹⁰¹ is PO₃H². In someembodiments, R¹⁰¹ is PO₃M¹ ₂. In some embodiments, R¹⁰¹ is PO₃M¹H. Insome embodiments, R¹⁰¹ is PO₄H₂. In some embodiments, R¹⁰¹ is PO₄M¹ ₂.In some embodiments, R¹⁰¹ is PO₄M¹H. In some embodiments, R¹⁰¹ is PO₄M².In some embodiments, R¹⁰¹ is C(O)NHOH. In some embodiments, R¹⁰¹ is NH₂.In some embodiments, R¹⁰¹ is NHR. In some embodiments, R¹⁰¹ is N(R)₂. Insome embodiments, R¹⁰¹ is NO₂. In some embodiments, R¹⁰¹ is COOR. Insome embodiments, R¹⁰¹ is CHO. In some embodiments, R¹⁰¹ is CH₂OH. Insome embodiments, R¹⁰¹ is OH. In some embodiments, R¹⁰¹ is OR. In someembodiments, R¹⁰¹ is SH. In some embodiments, R¹⁰¹ is SR. In someembodiments, R¹⁰¹ is C(O)N(R)₂. In some embodiments, R¹⁰¹ is C(O)NHR. Insome embodiments, R¹⁰¹ is C(O)NH₂. In some embodiments, R¹⁰¹ is halide.In some embodiments, R¹⁰¹ is tosylate. In some embodiments, R¹⁰¹ ismesylate. In some embodiments, R¹⁰¹ is SO₂NHR. In some embodiments, R¹⁰¹is triflate. In some embodiments, R¹⁰¹ is isocyanate. In someembodiments, R¹⁰¹ is cyanate. In some embodiments, R¹⁰¹ is thiocyanate.In some embodiments, R¹⁰¹ is isothiocyanate. In some embodiments, R¹⁰¹is R. In some embodiments, R¹⁰¹ is cyano. In some embodiments, R¹⁰¹ isCF₃. In some embodiments, R¹⁰¹ is Si(OR)₃.

In some embodiments, R¹⁰² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰² is CO₂H. In some embodiments, R¹⁰² is CO₂M¹. In someembodiments, R¹⁰² is CO₂R. In some embodiments, R¹⁰² is SO₃H. In someembodiments, R¹⁰² is SO₃M¹. In some embodiments, R¹⁰² is PO₃H². In someembodiments, R¹⁰² is PO₃M¹ ₂. In some embodiments, R¹⁰² is PO₃M¹H. Insome embodiments, R¹⁰² is PO₄H₂. In some embodiments, R¹⁰² is PO₄M¹ ₂.In some embodiments, R¹⁰² is PO₄M¹H. In some embodiments, R¹⁰² is PO₄M².In some embodiments, R¹⁰² is C(O)NHOH. In some embodiments, R¹⁰² is NH₂.In some embodiments, R¹⁰² is NHR. In some embodiments, R¹⁰² is N(R)₂. Insome embodiments, R¹⁰² is NO₂. In some embodiments, R¹⁰² is COOR. Insome embodiments, R¹⁰² is CHO. In some embodiments, R¹⁰² is CH₂OH. Insome embodiments, R¹⁰² is OH. In some embodiments, R¹⁰² is OR. In someembodiments, R¹⁰² is SH. In some embodiments, R¹⁰² is SR. In someembodiments, R¹⁰² is C(O)N(R)₂. In some embodiments, R¹⁰² is C(O)NHR. Insome embodiments, R¹⁰² is C(O)NH₂. In some embodiments, R¹⁰² is halide.In some embodiments, R¹⁰² is tosylate. In some embodiments, R¹⁰² ismesylate. In some embodiments, R¹⁰² is SO₂NHR. In some embodiments, R¹⁰²is triflate. In some embodiments, R¹⁰² is isocyanate. In someembodiments, R¹⁰² is cyanate. In some embodiments, R¹⁰² is thiocyanate.In some embodiments, R¹⁰² is isothiocyanate. In some embodiments, R¹⁰²is R. In some embodiments, R¹⁰² is cyano. In some embodiments, R¹⁰² isCF₃. In some embodiments, R¹⁰² is Si(OR)₃.

In some embodiments, R¹⁰⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰⁴ is CO₂H. In some embodiments, R¹⁰⁴ is CO₂M¹. In someembodiments, R¹⁰⁴ is CO₂R. In some embodiments, R¹⁰⁴ is SO₃H. In someembodiments, R¹⁰⁴ is SO₃M¹. In some embodiments, R¹⁰⁴ is PO₃H². In someembodiments, R¹⁰⁴ is PO₃M¹ ₂. In some embodiments, R¹⁰⁴ is PO₃M¹H. Insome embodiments, R¹⁰⁴ is PO₄H₂. In some embodiments, R¹⁰⁴ is PO₄M¹ ₂.In some embodiments, R¹⁰⁴ is PO₄M¹H. In some embodiments, R¹⁰⁴ is PO₄M².In some embodiments, R¹⁰⁴ is C(O)NHOH. In some embodiments, R¹⁰⁴ is NH₂.In some embodiments, R¹⁰⁴ is NHR. In some embodiments, R¹⁰⁴ is N(R)₂. Insome embodiments, R¹⁰⁴ is NO₂. In some embodiments, R¹⁰⁴ is COOR. Insome embodiments, R¹⁰⁴ is CHO. In some embodiments, R¹⁰⁴ is CH₂OH. Insome embodiments, R¹⁰⁴ is OH. In some embodiments, R¹⁰⁴ is OR. In someembodiments, R¹⁰⁴ is SH. In some embodiments, R¹⁰⁴ is SR. In someembodiments, R¹⁰⁴ is C(O)N(R)₂. In some embodiments, R¹⁰⁴ is C(O)NHR. Insome embodiments, R¹⁰⁴ is C(O)NH₂. In some embodiments, R¹⁰⁴ is halide.In some embodiments, R¹⁰⁴ is tosylate. In some embodiments, R¹⁰⁴ ismesylate. In some embodiments, R¹⁰⁴ is SO₂NHR. In some embodiments, R¹⁰⁴is triflate. In some embodiments, R¹⁰⁴ is isocyanate. In someembodiments, R¹⁰⁴ is cyanate. In some embodiments, R¹⁰⁴ is thiocyanate.In some embodiments, R¹⁰⁴ is isothiocyanate. In some embodiments, R¹⁰⁴is R. In some embodiments, R¹⁰⁴ is cyano. In some embodiments, R¹⁰⁴ isCF₃. In some embodiments, R¹⁰⁴ is Si(OR)₃.

In some embodiments, R¹⁰⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰⁵ is CO₂H. In some embodiments, R¹⁰⁵ is CO₂M¹. In someembodiments, R¹⁰⁵ is CO₂R. In some embodiments, R¹⁰⁵ is SO₃H. In someembodiments, R¹⁰⁵ is SO₃M¹. In some embodiments, R¹⁰⁵ is PO₃H². In someembodiments, R¹⁰⁵ is PO₃M¹ ₂. In some embodiments, R¹⁰⁵ is PO₃M¹H. Insome embodiments, R¹⁰⁵ is PO₄H₂. In some embodiments, R¹⁰⁵ is PO₄M¹ ₂.In some embodiments, R¹⁰⁵ is PO₄M¹H. In some embodiments, R¹⁰⁵ is PO₄M².In some embodiments, R¹⁰⁵ is C(O)NHOH. In some embodiments, R¹⁰⁵ is NH₂.In some embodiments, R¹⁰⁵ is NHR. In some embodiments, R¹⁰⁵ is N(R)₂. Insome embodiments, R¹⁰⁵ is NO₂. In some embodiments, R¹⁰⁵ is COOR. Insome embodiments, R¹⁰⁵ is CHO. In some embodiments, R¹⁰⁵ is CH₂OH. Insome embodiments, R¹⁰⁵ is OH. In some embodiments, R¹⁰⁵ is OR. In someembodiments, R¹⁰⁵ is SH. In some embodiments, R¹⁰⁵ is SR. In someembodiments, R¹⁰⁵ is C(O)N(R)₂. In some embodiments, R¹⁰⁵ is C(O)NHR. Insome embodiments, R¹⁰⁵ is C(O)NH₂. In some embodiments, R¹⁰⁵ is halide.In some embodiments, R¹⁰⁵ is tosylate. In some embodiments, R¹⁰⁵ ismesylate. In some embodiments, R¹⁰⁵ is SO₂NHR. In some embodiments, R¹⁰⁵is triflate. In some embodiments, R¹⁰⁵ is isocyanate. In someembodiments, R¹⁰⁵ is cyanate. In some embodiments, R¹⁰⁵ is thiocyanate.In some embodiments, R¹⁰⁵ is isothiocyanate. In some embodiments, R¹⁰⁵is R. In some embodiments, R¹⁰⁵ is cyano. In some embodiments, R¹⁰⁵ isCF₃. In some embodiments, R¹⁰⁵ is Si(OR)₃.

In some embodiments, R¹⁰⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, R¹⁰⁶ is CO₂H. In some embodiments, R¹⁰⁶ is CO₂M¹. In someembodiments, R¹⁰⁶ is CO₂R. In some embodiments, R¹⁰⁶ is SO₃H. In someembodiments, R¹⁰⁶ is SO₃M¹. In some embodiments, R¹⁰⁶ is PO₃H². In someembodiments, R¹⁰⁶ is PO₃M¹ ₂. In some embodiments, R¹⁰⁶ is PO₃M¹H. Insome embodiments, R¹⁰⁶ is PO₄H₂. In some embodiments, R¹⁰⁶ is PO₄M¹ ₂.In some embodiments, R¹⁰⁶ is PO₄M¹H. In some embodiments, R¹⁰⁶ is PO₄M².In some embodiments, R¹⁰⁶ is C(O)NHOH. In some embodiments, R¹⁰⁶ is NH₂.In some embodiments, R¹⁰⁶ is NHR. In some embodiments, R¹⁰⁶ is N(R)₂. Insome embodiments, R¹⁰⁶ is NO₂. In some embodiments, R¹⁰⁶ is COOR. Insome embodiments, R¹⁰⁶ is CHO. In some embodiments, R¹⁰⁶ is CH₂OH. Insome embodiments, R¹⁰⁶ is OH. In some embodiments, R¹⁰⁶ is OR. In someembodiments, R¹⁰⁶ is SH. In some embodiments, R¹⁰⁶ is SR. In someembodiments, R¹⁰⁶ is C(O)N(R)₂. In some embodiments, R¹⁰⁶ is C(O)NHR. Insome embodiments, R¹⁰⁶ is C(O)NH₂. In some embodiments, R¹⁰⁶ is halide.In some embodiments, R¹⁰⁶ is tosylate. In some embodiments, R¹⁰⁶ ismesylate. In some embodiments, R¹⁰⁶ is SO₂NHR. In some embodiments, R¹⁰⁶is triflate. In some embodiments, R¹⁰⁶ is isocyanate. In someembodiments, R¹⁰⁶ is cyanate. In some embodiments, R¹⁰⁶ is thiocyanate.In some embodiments, R¹⁰⁶ is isothiocyanate. In some embodiments, R¹⁰⁶is R. In some embodiments, R¹⁰⁶ is cyano. In some embodiments, R¹⁰⁶ isCF₃. In some embodiments, R¹⁰⁶ is Si(OR)₃.

In some embodiments, T¹ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T² is H. In some embodiments, T¹ is CO₂H. In someembodiments, T¹ is CO₂M¹. In some embodiments, T¹ is CO₂R. In someembodiments, T¹ is SO₃H. In some embodiments, T¹ is SO₃M¹. In someembodiments, T¹ is PO₃H². In some embodiments, T¹ is PO₃M¹ ₂. In someembodiments, T¹ is PO₃M¹H. In some embodiments, T¹ is PO₄H₂. In someembodiments, T¹ is PO₄M¹ ₂. In some embodiments, T¹ is PO₄M¹H. In someembodiments, T¹ is PO₄M². In some embodiments, T¹ is C(O)NHOH. In someembodiments, T¹ is NH₂. In some embodiments, T¹ is NHR. In someembodiments, T¹ is N(R)₂. In some embodiments, T¹ is NO₂. In someembodiments, T¹ is COOR. In some embodiments, T¹ is CHO. In someembodiments, T¹ is CH₂OH. In some embodiments, T¹ is OH. In someembodiments, T¹ is OR. In some embodiments, T¹ is SH. In someembodiments, T¹ is SR. In some embodiments, T¹ is C(O)N(R)₂. In someembodiments, T¹ is C(O)NHR. In some embodiments, T¹ is C(O)NH₂. In someembodiments, T¹ is halide. In some embodiments, T¹ is tosylate. In someembodiments, T¹ is mesylate. In some embodiments, T¹ is SO₂NHR. In someembodiments, T¹ is triflate. In some embodiments, T¹ is isocyanate. Insome embodiments, T¹ is cyanate. In some embodiments, T¹ is thiocyanate.In some embodiments, T¹ is isothiocyanate. In some embodiments, T¹ is R.In some embodiments, T¹ is cyano. In some embodiments, T¹ is CF₃. Insome embodiments, T¹ is Si(OR)₃.

In some embodiments, T² is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T² is H. In some embodiments, T² is CO₂H. In someembodiments, T² is CO₂M¹. In some embodiments, T² is CO₂R. In someembodiments, T² is SO₃H. In some embodiments, T² is SO₃M¹. In someembodiments, T² is PO₃H². In some embodiments, T² is PO₃M¹ ₂. In someembodiments, T² is PO₃M¹H. In some embodiments, T² is PO₄H₂. In someembodiments, T² is PO₄M¹ ₂. In some embodiments, T² is PO₄M¹H. In someembodiments, T² is PO₄M². In some embodiments, T² is C(O)NHOH. In someembodiments, T² is NH₂. In some embodiments, T² is NHR. In someembodiments, T² is N(R)₂. In some embodiments, T² is NO₂. In someembodiments, T² is COOR. In some embodiments, T² is CHO. In someembodiments, T² is CH₂OH. In some embodiments, T² is OH. In someembodiments, T² is OR. In some embodiments, T² is SH. In someembodiments, T² is SR. In some embodiments, T² is C(O)N(R)₂. In someembodiments, T² is C(O)NHR. In some embodiments, T² is C(O)NH₂. In someembodiments, T² is halide. In some embodiments, T² is tosylate. In someembodiments, T² is mesylate. In some embodiments, T² is SO₂NHR. In someembodiments, T² is triflate. In some embodiments, T² is isocyanate. Insome embodiments, T² is cyanate. In some embodiments, T² is thiocyanate.In some embodiments, T² is isothiocyanate. In some embodiments, T² is R.In some embodiments, T² is cyano. In some embodiments, T² is CF₃. Insome embodiments, T² is Si(OR)₃.

In some embodiments, T³ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T³ is H. In some embodiments, T³ is CO₂H. In someembodiments, T³ is CO₂M¹. In some embodiments, T³ is CO₂R. In someembodiments, T³ is SO₃H. In some embodiments, T³ is SO₃M¹. In someembodiments, T³ is PO₃H². In some embodiments, T³ is PO₃M¹ ₂. In someembodiments, T³ is PO₃M¹H. In some embodiments, T³ is PO₄H₂. In someembodiments, T³ is PO₄M¹ ₂. In some embodiments, T³ is PO₄M¹H. In someembodiments, T³ is PO₄M². In some embodiments, T³ is C(O)NHOH. In someembodiments, T³ is NH₂. In some embodiments, T³ is NHR. In someembodiments, T³ is N(R)₂. In some embodiments, T³ is NO₂. In someembodiments, T³ is COOR. In some embodiments, T³ is CHO. In someembodiments, T³ is CH₂OH. In some embodiments, T³ is OH. In someembodiments, T³ is OR. In some embodiments, T³ is SH. In someembodiments, T³ is SR. In some embodiments, T³ is C(O)N(R)₂. In someembodiments, T³ is C(O)NHR. In some embodiments, T³ is C(O)NH₂. In someembodiments, T³ is halide. In some embodiments, T³ is tosylate. In someembodiments, T³ is mesylate. In some embodiments, T³ is SO₂NHR. In someembodiments, T³ is triflate. In some embodiments, T³ is isocyanate. Insome embodiments, T³ is cyanate. In some embodiments, T³ is thiocyanate.In some embodiments, T³ is isothiocyanate. In some embodiments, T³ is R.In some embodiments, T³ is cyano. In some embodiments, T³ is CF₃. Insome embodiments, T³ is Si(OR)₃.

In some embodiments, T⁴ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T⁴ is H. In some embodiments, T⁴ is CO₂H. In someembodiments, T⁴ is CO₂M¹. In some embodiments, T⁴ is CO₂R. In someembodiments, T⁴ is SO₃H. In some embodiments, T⁴ is SO₃M¹. In someembodiments, T⁴ is PO₃H². In some embodiments, T⁴ is PO₃M¹ ₂. In someembodiments, T⁴ is PO₃M¹H. In some embodiments, T⁴ is PO₄H₂. In someembodiments, T⁴ is PO₄M¹ ₂. In some embodiments, T⁴ is PO₄M¹H. In someembodiments, T⁴ is PO₄M². In some embodiments, T⁴ is C(O)NHOH. In someembodiments, T⁴ is NH₂. In some embodiments, T⁴ is NHR. In someembodiments, T⁴ is N(R)₂. In some embodiments, T⁴ is NO₂. In someembodiments, T⁴ is COOR. In some embodiments, T⁴ is CHO. In someembodiments, T⁴ is CH₂OH. In some embodiments, T⁴ is OH. In someembodiments, T⁴ is OR. In some embodiments, T³ is SH. In someembodiments, T⁴ is SR. In some embodiments, T⁴ is C(O)N(R)₂. In someembodiments, T⁴ is C(O)NHR. In some embodiments, T⁴ is C(O)NH₂. In someembodiments, T⁴ is halide. In some embodiments, T⁴ is tosylate. In someembodiments, T⁴ is mesylate. In some embodiments, T⁴ is SO₂NHR. In someembodiments, T⁴ is triflate. In some embodiments, T⁴ is isocyanate. Insome embodiments, T⁴ is cyanate. In some embodiments, T⁴ is thiocyanate.In some embodiments, T⁴ is isothiocyanate. In some embodiments, T⁴ is R.In some embodiments, T⁴ is cyano. In some embodiments, T⁴ is CF₃. Insome embodiments, T⁴ is Si(OR)₃.

In some embodiments, T⁵ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T⁵ is H. In some embodiments, T⁵ is CO₂H. In someembodiments, T⁵ is CO₂M¹. In some embodiments, T⁵ is CO₂R. In someembodiments, T⁵ is SO₃H. In some embodiments, T⁵ is SO₃M¹. In someembodiments, T⁵ is PO₃H². In some embodiments, T⁵ is PO₃M¹ ₂. In someembodiments, T⁵ is PO₃M¹H. In some embodiments, T⁵ is PO₄H₂. In someembodiments, T⁵ is PO₄M¹ ₂. In some embodiments, T⁵ is PO₄M¹H. In someembodiments, T⁵ is PO₄M². In some embodiments, T⁵ is C(O)NHOH. In someembodiments, T⁵ is NH₂. In some embodiments, T⁵ is NHR. In someembodiments, T⁵ is N(R)₂. In some embodiments, T⁵ is NO₂. In someembodiments, T⁵ is COOR. In some embodiments, T⁵ is CHO. In someembodiments, T⁵ is CH₂OH. In some embodiments, T⁵ is OH. In someembodiments, T⁵ is OR. In some embodiments, T⁵ is SH. In someembodiments, T⁵ is SR. In some embodiments, T⁵ is C(O)N(R)₂. In someembodiments, T⁵ is C(O)NHR. In some embodiments, T⁵ is C(O)NH₂. In someembodiments, T⁵ is halide. In some embodiments, T⁵ is tosylate. In someembodiments, T⁵ is mesylate. In some embodiments, T⁵ is SO₂NHR. In someembodiments, T⁵ is triflate. In some embodiments, T⁵ is isocyanate. Insome embodiments, T⁵ is cyanate. In some embodiments, T⁵ is thiocyanate.In some embodiments, T⁵ is isothiocyanate. In some embodiments, T⁵ is R.In some embodiments, T⁵ is cyano. In some embodiments, T⁵ is CF₃. Insome embodiments, T⁵ is Si(OR)₃.

In some embodiments, T⁶ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H²,PO₃M¹ ₂. PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR,N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR,C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate,cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In someembodiments, T⁶ is H. In some embodiments, T⁶ is CO₂H. In someembodiments, T⁶ is CO₂M¹. In some embodiments, T⁶ is CO₂R. In someembodiments, T⁶ is SO₃H. In some embodiments, T⁶ is SO₃M¹. In someembodiments, T⁶ is PO₃H². In some embodiments, T⁶ is PO₃M¹ ₂. In someembodiments, T⁶ is PO₃M¹H. In some embodiments, T⁶ is PO₄H₂. In someembodiments, T⁶ is PO₄M¹ ₂. In some embodiments, T⁶ is PO₄M¹H. In someembodiments, T⁶ is PO₄M². In some embodiments, T⁶ is C(O)NHOH. In someembodiments, T⁶ is NH₂. In some embodiments, T⁶ is NHR. In someembodiments, T⁶ is N(R)₂. In some embodiments, T⁶ is NO₂. In someembodiments, T⁶ is COOR. In some embodiments, T⁶ is CHO. In someembodiments, T⁶ is CH₂OH. In some embodiments, T⁶ is OH. In someembodiments, T⁶ is OR. In some embodiments, T⁶ is SH. In someembodiments, T⁶ is SR. In some embodiments, T⁶ is C(O)N(R)₂. In someembodiments, T⁶ is C(O)NHR. In some embodiments, T⁶ is C(O)NH₂. In someembodiments, T⁶ is halide. In some embodiments, T⁶ is tosylate. In someembodiments, T⁶ is mesylate. In some embodiments, T⁶ is SO₂NHR. In someembodiments, T⁶ is triflate. In some embodiments, T⁶ is isocyanate. Insome embodiments, T⁶ is cyanate. In some embodiments, T⁶ is thiocyanate.In some embodiments, T⁶ is isothiocyanate. In some embodiments, T⁶ is R.In some embodiments, T⁶ is cyano. In some embodiments, T⁶ is CF₃. Insome embodiments, T⁶ is Si(OR)₃.

In some embodiments, R is methyl, ethyl, isopropyl, n-propyl, alkyl,haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or benzyl. In someembodiments, R is methyl. In some embodiments, R is ethyl. In someembodiments, R is isopropyl. In some embodiments, R is n-propyl. In someembodiments, R is alkyl. In some embodiments, R is haloalkyl. In someembodiments, R is cycloalkyl. In some embodiments, R isheterocycloalkyl. In some embodiments, R is aryl. In some embodiments, Ris benzyl.

In some embodiments, M¹ is selected from any alkali metal. In someembodiments, M¹ is Li, Na, K, Rb or Cs. In some embodiments, M¹ is Li.In some embodiments, M¹ is Na. In some embodiments, M¹ is K. In someembodiments, M¹ is Rb. In some embodiments, M¹ is Cs.

In some embodiments, M² is selected from any alkaline earth metal. Insome embodiments, M¹ is Be, Mg, Ca, Sr, Ba or Ra. In some embodiments,M¹ is Be. In some embodiments, M¹ is Mg. In some embodiments, M¹ is Ca.In some embodiments, M¹ is Sr. In some embodiments, M¹ is Ba. In someembodiments, M¹ is Ra.

An “alkyl” group refers, in some embodiments, to a saturated aliphatichydrocarbon, including straight-chain or branched-chain. In someembodiments, alkyl is linear or branched. In some embodiments, alkyl isoptionally substituted linear or branched. In some embodiments, alkyl ismethyl. In some embodiments alkyl is ethyl. In some embodiments, thealkyl group has 1-20 carbons. In some embodiments, the alkyl group has1-8 carbons. In some embodiments, the alkyl group has 1-7 carbons. Insome embodiments, the alkyl group has 1-6 carbons. In some embodiments,non-limiting examples of alkyl groups include methyl, ethyl, isopropyl,n-propyl, isobutyl, butyl, pentyl or hexyl. In some embodiments, thealkyl group has 1-4 carbons. In some embodiments, the alkyl group may beoptionally substituted by one or more groups selected from halide,hydroxy, alkoxy, carboxylic acid, aldehyde, carbonyl, amido, cyano,nitro, amino, alkenyl, alkynyl, aryl, azide, epoxide, ester, acylchloride and thiol.

A “cycloalkyl” group refers, in some embodiments, to a ring structurecomprising carbon atoms as ring atoms, which are saturated, substitutedor unsubstituted. In some embodiments the cycloalkyl is a 3-12 memberedring. In some embodiments the cycloalkyl is a 6 membered ring. In someembodiments the cycloalkyl is a 5-7 membered ring. In some embodimentsthe cycloalkyl is a 3-8 membered ring. In some embodiments, thecycloalkyl group may be unsubstituted or substituted by a halogen,alkyl, haloalkyl, hydroxyl, alkoxy, carbonyl, amido, alkylamido,dialkylamido, cyano, nitro, CO₂H, amino, alkylamino, dialkylamino,carboxyl, thio and/or thioalkyl. In some embodiments, the cycloalkylring may be fused to another saturated or unsaturated 3-8 membered ring.In some embodiments, the cycloalkyl ring is an unsaturated ring. Nonlimiting examples of a cycloalkyl group comprise cyclohexyl,cyclohexenyl, cyclopropyl, cyclopropenyl, cyclopentyl, cyclopentenyl,cyclobutyl, cyclobutenyl, cycloctyl, cycloctadienyl (COD), cycloctaene(COE) etc.

A “heterocycloalkyl” group refers in some embodiments, to a ringstructure of a cycloalkyl as described herein comprising in addition tocarbon atoms, sulfur, oxygen, nitrogen or any combination thereof, aspart of the ring. In some embodiments, non-limiting examples ofheterocycloalkyl include pyrrolidine, pyrrole, tetrahydrofuran, furan,thiolane, thiophene, imidazole, pyrazole, pyrazolidine, oxazolidine,oxazole, isoxazole, thiazole, isothiazole, thiazolidine, dioxolane,dithiolane, triazole, furazan, oxadiazole, thiadiazole, dithiazole,tetrazole, piperidine, oxane, thiane, pyridine, pyran, thiopyran,piperazine, morpholine, thiomorpholine, dioxane, dithiane, diazine,oxazine, thiazine, dioxine, triazine, and trioxane.

A “crown etheryl” group refers in some embodiments to a cyclic structurethat comprises several ether groups. In some embodiments, the cyclicstructure comprises a —CH₂CH₂O— repeating unit. In some embodiments, thecyclic structure optionally comprises a —CH₂CH₂NH— repeating unit. Insome embodiments, non-limiting examples of the cyclic structure hasbetween 4-10 repeating units. In some embodiments, the cyclic structureis substituted. Substitutions include but are not limited to: F, Cl, Br,I, C₁-C₅ linear or branched alkyl, C₁-C₅ linear or branched haloalkyl,C₁-C₅ linear or branched alkoxy, C₁-C₅ linear or branched haloalkoxy,CF₃, CN, NO₂, —CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃,—OCH₂Ph, —NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or — or—C(O)NH₂.

A cyclamyl, cyclenyl, 1,4,7-Triazacyclononanyl, hexacyclenyl, groupsrefer in some embodiment to cyclic structures that comprise severalrepeating units that contain alkylamino groups. In some otherembodiments, the cyclic structures are substituted.

Substitutions include but are not limited to: F, Cl, Br, I, C₁-C₅ linearor branched alkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear orbranched alkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂,—CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph,—NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or — or —C(O)NH₂.

A “cryptandyl” group refers in some embodiments to a three dimensionalstructure that comprises several ether and alkylamino groups. In someembodiments, the structure is a [2.2.2]Cryptand:N[CH₂CH₂CH₂CH₂OCH₂CH₂]₃N(1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane). In someembodiments, the cyclic structure is substituted. Substitutions includebut are not limited to: F, Cl, Br, I, C₁-C₅ linear or branched alkyl,C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branched alkoxy,C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂,NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH,—C(O)Ph, C(O)O-alkyl, C(O)H, or — or —C(O)NH₂.

As used herein, the term “aryl” refers to any aromatic ring that isdirectly bonded to another group and can be either substituted orunsubstituted. The aryl group can be a sole substituent, or the arylgroup can be a component of a larger substituent, such as in anarylalkyl, arylamino, arylamido, etc. Exemplary aryl groups include,without limitation, phenyl, tolyl, xylyl, furanyl, naphthyl, pyridinyl,pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, oxazolyl,isooxazolyl, pyrazolyl, imidazolyl, thiophene-yl, pyrrolyl,phenylmethyl, phenylethyl, phenylamino, phenylamido, etc. Substitutionsinclude but are not limited to: F, Cl, Br, I, C₁-C₅ linear or branchedalkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branchedalkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂,NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH,—C(O)Ph, C(O)O-alkyl, C(O)H, or — or —C(O)NH₂.

In some embodiments, the term “halide” used herein refers to anysubstituent of the halogen group (group 17). In some embodiments, halideis fluoride, chloride, bromide or iodide. In some embodiments, halide isfluoride. In some embodiments, halide is chloride. In some embodiments,halide is bromide. In some embodiments, halide is iodide.

In some embodiments, “haloalkyl” refers to alkyl, alkenyl, alkynyl orcycloalkyl substituted with one or more halide atoms. In someembodiments, haloalkyl is partially halogenated. In some embodimentshaloalkyl is perhalogenated (completely halogenated, no C—H bonds). Insome embodiments, haloalkyl is CH₂CF₃. In some embodiments. haloalkyl isCH₂CCl₃. In some embodiments, haloalkyl is CH₂CBr₃. In some embodiments,haloalkyl is CH₂CI₃. In some embodiments, haloalkyl is CF₂CF₃. In someembodiments, haloalkyl is CH₂CH₂CF₃. In some embodiments, haloalkyl isCH₂CF₂CF₃. In some embodiments, haloalkyl is CF₂CF₂CF₃. In someembodiments, the haloalkyl group may be optionally substituted by one ormore groups selected from halide, hydroxy, alkoxy, carboxylic acid,aldehyde, carbonyl, amido, cyano, nitro, amino, alkenyl, alkynyl, aryl,azide, epoxide, ester, acyl chloride and thiol.

In some embodiments, the term “benzyl” used herein refers to a methylene(CH₂, CHR or CR₂) connected to an “aryl” (described above) moiety. Insome embodiments, the methylene is non-substituted (CH₂). In someembodiments, the methylene is substituted (CHR or CR₂). In someembodiments, the methylene is substituted with alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl, benzyl or any combination of suchmoieties.

In some embodiments, X¹ is S, O or CH₂. In some embodiments, X¹ is S. Insome embodiments, X¹ is O. In some embodiments, X¹ is CH₂.

In some embodiments, X² is S, O or CH₂. In some embodiments, X² is S. Insome embodiments, X² is O. In some embodiments, X² is CH₂.

In some embodiments, X³ is S, O or CH₂. In some embodiments, X³ is S. Insome embodiments, X³ is O. In some embodiments, X³ is CH₂.

In some embodiments, X⁴ is S, O or CH₂. In some embodiments, X⁴ is S. Insome embodiments, X⁴ is O. In some embodiments, X⁴ is CH₂.

FIG. 5A is a high-level schematic illustration of bonding molecules 116forming a surface molecules layer 117 on anode 100 and/or anode activematerial particles 110, according to some embodiments of the invention.It is emphasized that FIG. 5A is highly schematic and representsprinciples for selecting bonding molecules 116, according to someembodiments of the invention. Actual bonding molecules 116 may beselected according to requirements, e.g., from bonding molecules 116represented by any one of formulas I-VII, under any of theirembodiments.

FIG. 5B is a high-level schematic illustration of non-limiting examplesfor bonding molecules 116, according to some embodiments of theinvention. Non-limiting examples for bonding molecules 116 include anyof the following: lithium 4-methylbenzenesulfonate, lithium3,5-dicarboxybenzenesulfonate, lithium sulfate, lithium phosphate,lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium4-dodecylbenzenesulfonate, lithium propane-1-sulfonate, lithium1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate,lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium2,6-di-tert-butylbenzene-1,4-disulfonate,3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide),3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide),lithium aniline sulfonate (the sulfonate may be in any of para, meta andortho positions) as well as poly(lithium-4-styrenesulfonate) applied incoating the anode material particles. It is noted that in cases ofcoatings that contain lithium (e.g., metallic lithium), ionic liquidadditive(s) 135 may be selected to be not reactive toward it.

For example, various coatings of the anode active material may be usedto bond or enhance bonding of molecules 116 to anode material 110, asdisclosed above. The size(s) of molecules 116 may be selected to providegood lithium ion conductivity therethrough. In certain embodiments,molecules 116 may be selected (e.g., some of the disclosed salts) toform channels configured to enable fast lithium ion movementtherethrough.

Surface molecules layer 117 may be configured to prevent contact ofelectrolyte solvent (of electrolyte 85) with anode active material 110,e.g., through steric hindrance by molecules 116. Non-limiting examplesare embodiments represented e.g., by formulas II, IV and V, amongothers, such as the non-limiting examples lithium3,5-dicarboxybenzenesulfonate, lithium2,6-di-tert-butylbenzene-1,4-disulfonate,3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide),3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), etc.

Molecules 116 may be selected and attached onto anode active material110 in a way that forms a mechanical and/or electrostatic barriertowards electrolyte solvent and prevents it from reaching andinteracting with anode active material 110. Bonding molecules 116 may beselected to have electron rich groups that provide mobile electriccharge on the surface of molecules layer 117. Non-limiting examples areembodiments represented e.g., by formulas II, and IV-VII, havingconjugated double bonds, acidic groups and benzene groups, among others,such as the non-limiting examples lithium 4-methylbenzenesulfonate,lithium 3,5-dicarboxybenzenesulfonate, lithium2,6-dimethylbenzene-1,4-disulfonate,3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide),3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N hydroxypropanamide),lithium aniline sulfonate, poly(lithium-4-styrenesulfonate) etc.

For example, bonding molecules 116 may be selected to have a width W(anchored in anode 100 and/or anode active material particles 110) of upto three benzene rings and a length L (protruding into electrolyte 105)of up to four benzene rings, as exemplified in a non-limiting manner inembodiments represented e.g., by formulas II and VII having bicyclic ortricyclic structures, e.g., anthracene-based structures and/or inembodiments represented e.g., by formulas IV and V.

In some embodiments, bonding molecules 116 may comprise an anodematerial anchoring part 116A, configured to bind to or be associatedwith anode active material 110, e.g., via lithium, thiols, or otherfunctional groups in bonding molecules 116. In some embodiments, anodematerial anchoring part 116A may be pre-lithiated exemplified in anon-limiting manner in embodiments represented by any of formulas I-VIIwhich include lithium, such as the non-limiting examples illustrated inFIG. 5B.

In some embodiments, bonding molecules 116 may comprise an ionicconductive part 116B having an ionic conductivity which is much higherthan its electronic conductivity, e.g., by one, two, three or moreorders of magnitude. Ionic conductive part 116B may extend through mostor all of length L of bonding molecules 116 and provide a conductivitypath 91A (illustrated schematically) for lithium ions 91 moving back andforth between electrolyte 105 and anode 110 during charging anddischarging cycles. Conductivity paths 91A may be provided e.g., byconjugated double bonds, acidic groups, benzene rings, carbon-fluorinebonds, charged functional groups etc. which are disclosed above. Forexample, the charge distribution on bonding molecules 116 may beselected to be mobile and support lithium ion movement across moleculeslayer 117, possibly reducing the charge of the lithium ion to Li^(δ+) asexplained above, to prevent metallization on the surface of anode 110.Partial charge reduction may be carried out by electron rich groups suchas aromatic groups and acidic groups disclosed above.

In some embodiments, bonding molecules 116 may comprise a top, ionicliquid binding part 116C configured to bind cations 132 and/or anions131 of ionic liquid additive 135 in electrolyte 105. For example,embodiments represented by any of formulas I-VII which involve chargedand/or polar functional groups may provide top, ionic liquid bindingpart 116C, e.g., lithium 3,5-dicarboxybenzenesulfonate, lithium sulfate,lithium phosphate, lithium phosphate monobasic, lithiumtrifluoromethanesulfonate, lithium1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate,lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium2,6-di-tert-butylbenzene-1,4-disulfonate,3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide),3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide),lithium aniline sulfonate (the sulfonate may be in any of para, meta andortho positions) as well as poly(lithium-4-styrenesulfonate), as somenon-limiting examples. Ionic liquid binding part 116C may be furtherconfigured to stabilize electrolyte-buffering zone(s) 130 as describedabove.

FIG. 6 is a high-level schematic illustration of bonding molecules 116forming surface molecules layer 117 on anode 100 and/or anode activematerial particles 110, according to some embodiments of the invention.In the illustrated non-limiting example, bonding molecules 116 comprisea combination of lithium borates 102A which anchor (116A) layer 117 toanode active material 110, and polymer molecules (116B) having electronrich groups (e.g., conjugated bonds, acidic groups, etc.) which provide,together with lithium borates interconnecting the polymer molecules,ionic conductivity paths 91A through layer 117 and have an ionicconductivity which is much larger than electronic conductivity (e.g., byone or few orders of magnitude). Either or both the lithium boratemolecules and the polymer molecules may have electron rich groups andmay be pre-lithiated. Surface molecules layer 117 may comprise multiplepolymer layers interconnected by lithium borates. Surface moleculeslayer 117 may bond cations 132 and/or anions 131 of ionic liquid(additive) at its top layer 116C, yet may also operate withcarbonate-based electrolyte 85 due to its efficient blocking of contactbetween the solvent of electrolyte 85 and anode active material 110. Itis noted that lithium borates and lithium phosphates 102A may likewisebe used similarly to Li₂B₄O₇, which is provided in FIG. 6 as anon-limiting example.

FIG. 7 is a high-level schematic illustration of bonding molecules 116forming thick surface molecules layer 117 on anode 100 and/or anodeactive material particles 110, according to some embodiments of theinvention. In certain embodiments, bonding molecules 116 may extend deepinto electrolyte 105 to form thick surface molecules layer 117 having alength L of more than ten benzene rings. For example, surface layer 117may be thick to an extent of 10% or more of the distance between anode100 and separator 86. The charge distribution on bonding molecules 116in ionic conductive part 116B may be selected to be mobile and supportlithium ion movement across molecules layer 117, possibly reducing thecharge of the lithium ion to Li^(δ+) as explained above, to preventmetallization on the surface of anode 110. Partial charge reduction maybe carried out by electron rich groups such as aromatic groups andacidic groups disclosed above. Certain embodiments comprise surfacemolecules layer 117 having intermediate thickness of between 4-10benzene rings.

FIGS. 8A and 8B are high-level schematic illustrations of a lithium ioncell 150 with electrolyte 105 during charging, according to someembodiments of the invention. Lithium ion cell 150 comprises a metalloidanode 100, comprising at least one of C, graphite, Si, Sn, Ge and Al,and electrolyte 105 comprising at most 20% of at least one ionic liquidas ionic liquid additive 135. Ionic liquid additive 135 may form amobile SEI (e.g., in place of the (static) SEI, in addition to the SEIor in an interaction with the SEI) on anode 100, e.g., during charging,as illustrated in FIG. 8A and disclosed above.

In certain embodiments, electrolyte 105 may comprise at most 5% of theat least one ionic liquid. In certain embodiments, the at least oneionic liquid may comprise sulfonylimides-piperidinium derivatives ionicliquid(s). Ionic liquid additive 135 may be selected to have a meltingtemperature below 10° C., below 0° C. or below −4° C., in certainembodiments.

Layer 145 may be part of the anode surface or coated thereupon, and bindat least a part of ionic liquid additive 135 to hold at least stationaryportion 140A of ionic liquid additive 135 at the anode surface tosupport the SEI, prevent decomposition of electrolyte 105 and preventlithium metallization on anode 100. Layer 145 of bonding molecules 116and/or layer 140A of bonded ionic liquid additive may also provide somenegative electric charge that partly reduces the lithium ion, leavingthem with a partial charge δ+ and preventing full reduction andmetallization of lithium on the anode surface. Layer 145 of bondingmolecules 116 and/or layer 140A of bonded ionic liquid additive may beconfigured to support gradient 119 described in FIG. 3A.

FIG. 9 is a high-level flowchart illustrating a method 200, according tosome embodiments of the invention. The method stages may be carried outwith respect to cells 150 described above and lithium ion batteriesconstructed therefrom, which may optionally be configured to implementmethod 200. Method 200 may comprise stages for producing, preparingand/or using cells 150, such as any of the following stages,irrespective of their order.

Method 200 may comprise adding up to 20% of at least one ionic liquid toan electrolyte used in lithium ion batteries (stage 210), usingmetalloid-based anodes (stage 215), e.g., comprising at least one of C,graphite, Si, Sn, Ge and Al, and using the electrolyte with the ionicliquid additive to prevent lithium metallization in lithium ionbatteries (stage 220). Method 200 may comprise selecting one or moreionic liquids to have cations and/or anions which are much larger thanlithium ions, e.g., two to ten times the size (e.g., volume) thereof(stage 212). In certain embodiments, electrolyte 105 may comprise atmost 5% of the at least one ionic liquid. In certain embodiments, the atleast one ionic liquid may comprise sulfonylimides-piperidiniumderivatives ionic liquid(s). Ionic liquid additive 135 may be selectedto have a melting temperature below 10° C., below 0° C. or below −4° C.

In certain embodiments, method 200 may comprise forming a surface layeron the anode to bond (e.g., electrostatically and/or ionically) at leastsome of the ionic liquid additive(s) (stage 230), e.g., by coating theanode active material by various bonding molecules as disclosed aboveand/or partly or fully pre-coating and/or coating the active materialusing corresponding polymers (stage 235).

Method 200 may comprise carrying out the bonding during at least a firstcharging cycle of the cell (stage 240), possibly during several firstcharging and discharging cycles. In certain embodiments, the bonding ofcations and/or anions may be carried out, at least partially, on theactive material itself, even before the first charging cycle. Thebonding of the ionic liquid to the bonding layer may be electrostaticand/or salt-like (ionic). In certain embodiments, the bonding may be atleast partly covalent.

Method 200 may comprise stabilizing the SEI of the cell through thebonded portion of the ionic liquid additive(s) to the surface layer(stage 250).

Method 200 may further comprise configuring the bonding molecules toprevent contact of electrolyte solvent with anode active material, e.g.,through steric hindrance (stage 260).

Method 200 may further comprise configuring the bonding molecules tohave electron rich groups that provide mobile electric charge on thesurface of molecules layer (stage 270), e.g., to provide an ionicconductivity path through the surface molecules layer (stage 275).

Method 200 may further comprise pre-lithiating the anode active materialthrough an anode material anchoring part of the bonding molecules (stage280).

Method 200 may comprise using anchored and interconnected conductivepolymer molecules as the surface layer (stage 290). Alternatively orcomplementarily, method 200 may comprise using a thick surface layerthat protrudes significantly into the electrolyte (stage 295).

FIGS. 10A and 10B are non-limiting examples which indicate reversiblelithiation at the anode when using the ionic liquid additive accordingto some embodiments of the invention (FIG. 10A) with respect to theprior art (FIG. 10B). Charging and discharging cycles at IC (ca. 1 hourcharging followed by 1 hour discharging) are shown for half-cells havinganodes 100 operate with lithium as cathodes 87—in FIG. 10A with ionicliquid additive 135 being N,N-Diethyl-N-methyl-N-propylammonium (cation132) and bis(fluorosulfonyl)imide (anion 131) (electrolyte 105, with 1%ionic liquid additive 135) and in FIG. 10B without ionic liquid additive135 (electrolyte 85—FEC:DMC (3:7) and 2% VC). The cycles were performedafter four formation cycles at 0.03 C (discharge to 80% of the capacity)followed by one cycle at 0.1 C, limited by capacity. Without being boundby theory, the continuous rise in the discharge voltage from cycle tocycle (while the capacity during charging and discharging remainsconstant at ca. 600 mAh/gr) in FIG. 10A (in contrast to FIG. 10B) isunderstood as indicating the reversibility of lithium excess in theanode (e.g., lithiated lithium during the first slow cycles) facilitatedthrough the ionic liquid additive preventing the lithium ions frombinding to the anode active material permanently and/or possiblycontributing to formation of a relatively lithium poor SEI.

Embodiments of the present invention provide efficient and economicalmethods and mechanisms for pre-lithiating anodes of lithium ion batterycells, and thereby provide improvements to the technological field ofenergy storage devices. Pre-lithiation methods and pre-lithiated cellsfor lithium ion batteries are provided. In the methods, lithium powderis mixed with an ionic liquid, the mixture is suspended in anelectrolyte, and the suspension is introduced into the cell. The ionicliquid may be removed from the cell prior to operation, or may bemaintained as an electrolyte additive which provides a mobile SEI (solidelectrolyte interface), and/or an immobilize MSEI (mobile SEI), duringoperation of the cell. The pre-lithiation may be carried out in aformation process and/or during operation of the cell.

FIG. 11 is a high-level schematic block diagram of a prelithiationmethod 300 applied to a lithium ion battery 150, according to someembodiments of the invention. FIG. 11 illustrates schematically on itsleft-hand side, prelithiation method 300 comprising mixing lithiumpowder 305 with an ionic liquid 135 to form a mixture 315 (stage 310),suspending mixture 315 in an electrolyte 85 (e.g., carbonate-basedelectrolyte) to form a suspension 325 (stage 320), and introducingsuspension 325 into a cell 150 (stage 330). FIG. 11 further illustrateson its right-hand side, a schematic side view of anodes 100 (denoted“A”), separators 86 (denoted “S”) and cathodes 87 (denoted “C”) in cell150. It is noted that the figures are very schematic, and merely relateto the ordering of some of the elements of the battery, withoutreflecting realistic spatial relations, for the sake of clarity ofexplanation. Electrolyte 105 (denoted “E”, which may be carbonate-basedand possibly include ionic liquid additive(s)) contacts anodes 100 andcathodes 87 in separate compartments, delimited by separators 86, afeature which is not shown in the figures. Current collectors 82, 84 aredepicted for anode 100 and cathode 87, respectively, e.g., innon-limiting examples, anode current collector 82 may be made of copperand/or copper alloys and cathode current collector 84 may be made ofaluminum and/or aluminum alloys. Electrolyte 105 may comprise somelithium powder 305, or lithium powder 305 may be attached to anode(s)100 during a formation process. Ionic liquid 135 may remain inelectrolyte 85 and function as a mobile SEI (MSEI), as disclosed e.g.,above, or some or all of ionic liquid 135 may be removed from cell 150,with electrolyte 85 possibly being replaced before operation byelectrolyte 105 or by a different electrolyte. It is noted that ionicliquids may generally comprise one or more salt(s) which are liquidbelow 100° C., or even at room temperature or at lower temperatures suchas below any of 10° C., 0° C., −5° C., −10° C., etc.

In contrast to prior art practice of mixing lithium powder (comprisingmicrometer particles with bonded polymer) in the anode slurry to producepre-lithiate anode(s) 100, disclosed embodiments, utilize electrolyte105, and in particular a coupling of ionic liquid additive 135 toelectrolyte 85, to associate lithium powder 305 thereto and, within cell150 and possibly before and/or during the formation process,pre-lithiate anode(s) 100 from lithium powder 305. Ionic liquid additive135 may be maintained in cell 150—in electrolyte 105 and/or at leastpartly bonded to anode(s) 100, and possibly function to improve thesafety and lifetime of battery 150, as disclosed below.

In certain embodiments, lithium powder 305 may comprise uncoated lithiumpowder 305, which may have nanometer to micrometer particles. Uncoatedlithium particles may bond (or be configured to bond) better to ionicliquid 135. For example, lithium powder 305 may be prepared along linesderived from the method of Zhao et al. 2015 (Artificial SolidElectrolyte Interphase-Protected LixSi Nanoparticles: An Efficient andStable Prelithiation Reagent for Lithium-Ion Batteries, J. Am. Chem.Soc., 2015, 137 (26), pp 8372-8375), without using silicon.

Ionic liquid 135 may then be used to suspend lithium powder 305 inelectrolyte 85 to form suspension 325, possibly replacing in thisfunction polymer coating of the lithium powder particles. Following theintroduction of suspension 325 into cell 150, at least some of thelithium may enter anode(s) 100 operatively to reduce or prevent thecapacitance decrease of operating cells, and ionic liquid 135 may thenfunction in operative cell 150 for forming the MSEI.

Ionic liquid 135 may be selected to be non-reactive (or possiblysomewhat reactive) towards lithium, and the length of chains of theanions is selected to optimize suspension 325. Suspension 325 may beused for pre-lithiation only (be washed away before operation) or ionicliquid 135 may be retained in the operative cell. Non-limiting examplesfor ionic liquid 135 are disclosed herein.

FIG. 12 is a high-level flowchart illustrating a method 300, accordingto some embodiments of the invention. The method stages may be carriedout with respect to cells 150 described above, which may optionally beconfigured to implement method 300.

Method 300 may comprise stages for producing, preparing and/or usingcells 150, such as any of the following stages, irrespective of theirorder. In various embodiments, method 300 and/or stages thereof may beimplemented as part of any of methods 200 and/or 400 disclosed herein.

Method 300 may comprise mixing lithium powder with an ionic liquid(stage 310), suspending the mixture in an electrolyte (stage 320), andintroducing the suspension into the cell (stage 330). Method 300 maycomprise pre-lithiating anodes by the suspended lithium (stage 340),e.g., in a formation process and/or during operation.

Method 300 may further comprise replacing the electrolyte for celloperation (stage 350).

In certain embodiments, particles of lithium powder 305 may beun-coated. In certain embodiments, particles of lithium powder 305 maybe 10-100 nm in diameter.

Certain embodiments comprise composite electrolytes for lithium ioncells and corresponding cells, production processes and methods. Thecomposite electrolytes comprise solid electrolyte particles coated byflexible ionic conductive material. The flexible ionic conductivematerial is selected to increase a contact area between the solidelectrolyte particles and electrode active material particles withrespect to a contact area therewith of uncoated solid electrolyteparticles, and/or to provide an ionic conduction path through theflexible ionic conductive material throughout at least a portion of thecomposite electrolyte. The flexible ionic conductive material mayfurther comprise bonding molecules selected to bind electrode activematerial particles and/or to ionic liquid ions serving as additionalelectrolyte in the cell. Disclosed semi-solid electrolyte cells are ableto provide high ionic conductivity and cell operation at a widetemperature range, extending to 0° C., −10° C., −20° C. or even −40° C.Disclosed composite electrolytes may also be described as semi-solidelectrolytes due to their flexibility and compliance to appliedpressures, which secure better contact between the electrolyte and theelectrodes.

FIGS. 13A and 13B are high-level schematic illustrations of lithium ioncells 150, according to some embodiments of the invention. FIG. 13C is ahigh-level schematic illustration of prior art lithium ion cells 90.Disclosed cells 150 comprise at least one film of composite electrolyte120 contacting an anode 100 and/or a cathode 87 of cell 150, replacingat least partly prior art liquid electrolyte 85. Other elements of priorart lithium ion cells 90, such as a separator 86, current collectors 82,84, enclosure 79 and even anode 95 and cathode 87 may be used indisclosed cells 150 or replaced by corresponding elements as disclosedherein, e.g., modified anode 100, modified cathode 87, modifiedenclosure 160 and possibly modified current collectors (not shown).Composite electrolyte 120 may be used to replace electrolyte 85 andseparator 86 to form a continuous solid or semi-solid contact from anode100 to cathode 87, as illustrated schematically in FIG. 13A, orcomposite electrolyte 120 may be used to replace only part ofelectrolyte near either or both anode 100 and cathode 87, leaving someliquid electrolyte 85 and separator 86 therebetween, as illustratedschematically in FIG. 13B.

FIGS. 14A and 14B are high-level schematic illustrations of the contactbetween an electrode and composite electrolyte 120, according to someembodiments of the invention. FIG. 14C is a high-level schematicillustration of prior art contact between an electrode 95 and a solidelectrolyte 83. The disclosed electrode is illustrated in a non-limitedmanner as anode 100, and similar principles may apply to cathode 87 aswell.

Electrode active material particles 110 are illustrated schematically ascircles at an interface 113 to composite electrolyte 120. It is notedthat the interface between anode 100 and electrolyte 120 is denoted by113 while the surface of anode material particles 110 is denoted by 112.The considerations disclosed below may by applicable to either interface113 and/or surface 112, depending on details of the interaction models,and are hence treated as alternatives through the disclosure. Compositeelectrolyte particles 125 may comprise solid particles 122 of compositeelectrolyte 120, illustrated schematically as circles, which have anionic conductive coating 124 at least partly enveloping solid particles122. Coating 124 may be flexible and yield upon contact of activematerial particles 110 with particles 122 and/or upon application ofpressure thereupon (e.g., pressure 160A which may be applied onenclosure 160 mechanically, thermally or by letting gases evaporate outof enclosure 160). It is emphasized that electrolyte 120 is configuredto have minimal porosity to ensure good contact among electrode activematerial particles 110 to maximize ionic conductivity and to increasethe energy density of cells 150. Moreover, the porosity at interfaceregion 113 between electrolyte 120 and electrode(s) 100 and/or 87 and/orthe porosity of electrode material particle surface 112 is configured tobe minimal to ensure good contact between the electrode active materialparticles and the electrolyte particles to maximize ionic conductivityand to increase the energy density of cells 150.

In contrast to prior art interfaces 83A which provide minimal contact81A between hard active material particles 95A and solid electrolyteparticles 88, due to the rigid nature of particles 95A, 88, disclosedcomposite electrolyte particles 125 provide a much broader contact 121Aproviding a larger contact area between composite electrolyte particles125 and active material particles 110 to enable much better ion transfertherebetween. As a result, the ionic conductivity at interface 113between disclosed composite electrolyte 120 and anode 100 (and/orthrough electrode material particle surface 112) is much high along aconductivity path 121 (indicated schematically by the broken line arrow)than prior art ionic conductivity at interface 83A between prior artsolid electrolyte 83 and anode 95 along a conductivity path 81(indicated schematically by the broken line arrow). The resultingimprovement in ionic conductivity may reach one or more orders ofmagnitude, as composite electrolyte particles 125 provide a contact area121A with active material particles 110 which may be one or more ordersof magnitude larger than contact area 81A of prior art solid electrolyteparticles 88 and active material particles 95A.

Additionally, ionic conductive coating 124 may be configured to providean additional conductivity path 123 for delivering lithium ions betweenthe electrode (e.g., anode 100) and composite electrolyte 120, inaddition to prior art path 81 through contact area 81A therebetween. Forexample, ionic conductive coating 124 may comprise a plurality oflithium ion binding sites which are separated from each other by 2-3 nmor less, to conduct the lithium ions.

Without being bound by theory, prior art ionic conduction depends oncracks in solid electrolyte particles 88 and therefore also depends oncontact area 81A between solid electrolyte particles 88 and hard activematerial particles 95A. In addition to achieving improved ionicconductivity path 121 by providing increased contact area 121A,disclosed composite electrolyte also provides additional conductivitypath 123 through flexible ionic conductive coating 124, which may beconfigured to build a continuous network throughout at least parts ofcomposite electrolyte 120 that supports conductivity path 123independently from conductivity path 121—to further enhance and makerobust the ionic conductivity between electrodes 100, 87 and compositeelectrolyte 120.

FIGS. 14D-14H are high-level schematic illustrations of interfaces 113between any of electrode active material 110, 110A, 110B and electrolyteparticles 122, 125, according to some embodiments of the invention.Electrode active material 110 is represented in a non-limiting manner asanode active material 110, yet similar principles may apply to cathodeactive material as well. The disclosed electrode is illustrated in anon-limited manner as anode 100, and similar principles may apply tocathode 87 as well. It is noted that the disclosed considerations may beapplicable to interface 113 and/or to the interface of electrolyte 120with surface 112 of anode material particles 110.

In some embodiments (see e.g., FIG. 14D), composite electrolyte 120 maycomprise electrolyte particles 122 embedded in a viscous ionic liquid126, configured to improve contact 121A and ionic conductivity betweenanode 100 and composite electrolyte 120 and possibly provide alternativeionic conduction path 123A.

In some embodiments (see e.g., FIG. 14E), active material particles 110may be coated by ionic conductive coating 134, prior to incorporationthereof in the electrode slurry, in the electrode slurry itself, orpossibly after preparation of the electrode (in the latter case, ionicconductive coating 134 may only enclose active material particles 110partially). Examples for coatings 134 are presented above (see e.g.,FIG. 1B).

In some embodiments, (see e.g., FIG. 14F), both active materialparticles 110 may be coated by ionic conductive coating 134, and solidelectrolyte particles 122 may be coated by ionic conductive coating 124,as disclosed above. It is noted that either or both active materialparticles 110 and electrolyte particles 122 may be coated by ionicconductive coatings 134, 124, to form particles 110B, 125 respectively,and/or by flexible coatings 134, 124, to possibly provide an additionalion conduction path beyond particles 122 (and cracks therein) themselvesand/or to increase the contact area between active material particles110 and electrolyte particles 122 to enhance ionic conductiontherethrough.

In some embodiments, illustrated schematically in FIGS. 14G and 14H,coatings 124 may comprise bonding molecules 129 which may be selected toenhance adhesion of electrolyte particles 125 to the electrode (e.g., toany of anode active material particles 110, 110A, 110B) and/or enhanceionic conduction between the electrode (e.g., anode 100) and compositeelectrolyte 120 by increasing the contact area therebetween and/or byproviding additional path(s) for ionic conduction therebetween. In someembodiments, illustrated schematically in FIG. 14H, bonding molecules129 may be configured to bind cations 131 (or anions 132) of ionicliquid 135 used either as liquid electrolyte 85 and/or 105 (see FIG.13B) or as an ionic liquid additive to liquid electrolyte 85 and/or105—e.g., as disclosed herein Examples for bonding molecules 129 maycomprise e.g., lithium 3,5-dicarboxybenzenesulfonate, lithium sulfate,lithium phosphate, lithium phosphate monobasic, lithiumtrifluoromethanesulfonate, lithium1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate,lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium2,6-di-tert-butylbenzene-1,4-disulfonate,3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide),3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide),lithium aniline sulfonate (the sulfonate may be in any of para, meta andortho positions) as well as poly(lithium-4-styrenesulfonate), as well asrelated molecules derived therefrom by various substitutions andmodifications, provided as some non-limiting examples.

It is emphasized that elements illustrated in FIGS. 13A, 13B, 14A, 14Band 14D-14H may be combined to provide additional embodiments which arenot illustrated explicitly, such as additional combinations of one ormore ionic conductive coatings 124, 134 and/or viscous ionic liquid 126.

FIGS. 15A-15C are a high-level schematic block diagrams of variousproduction methods 151, according to some embodiments of the invention.Electrolyte 120 may be processed to be incorporated in cells 150 invarious, alternative or complementary ways, such as contact electrolytesolution or slurry with porous electrode(s) 120A, addition ofelectrolyte material to the electrode material 120B, addition ofelectrolyte slurry into the electrode slurry 120C, and/or attaching asolid electrolyte layer onto the electrode 120D, as disclosed below(FIGS. 15A, 15B). Ionic conductive material 122 may be used forelectrolyte 120 and/or ionic conductive coating(s) 124 such as ionicconductive polymers may be applied to electrolyte particles at variousprocess stages with respect to the incorporation of the electrolyte inthe cell (120A-120D).

It is emphasized that while anodes 100 may be porous during thepreparation processes, the porosity of the resulting anode 100 and theporosity at interface region 113 between electrolyte 120 and anode 100(and/or the porosity of electrode material particle surface 112) areconfigured to be minimal to ensure good contact between the electrodeactive material particles and the electrolyte particles to maximizeionic conductivity and to increase the energy density of cells 150.

Electrode active material particles and additives 152 (e.g., electronconductive additives 152A, binder(s), monomers and/or polymers) may beprocessed into an electrode slurry 155, e.g., by ball milling activematerial particles and additives 152 and possibly adding liquid, fromwhich electrodes, e.g., anodes 100 and cathodes 87 are produced, e.g.,by spreading and drying (see e.g., FIG. 1B and process 111 below).Electrode slurry 155 and the electrode production process parameters maybe configured to provide a predefined level of porosity to theelectrode, e.g., >70%. The electrode porosity may be configured toprovide good electrolyte contact to the active material 155, e.g., incases electrolyte 120 is introduced in solution (120A) and followingevaporation of the sustaining liquid 158 (e.g., solvent). Possiblypressure 157 may be applied to improve contact 155, possibly by pressing160A (see FIG. 14A) cells 150. Processes 151 may be further configuredand optimized to prepared electrolyte 120 to have minimal porosity toensure good contact among electrode active material particles 110 tomaximize ionic conductivity and to increase the energy density of cells150.

In certain embodiments, production methods 151 comprise adding at leastsome of the electrolyte material as additive 120B (FIG. 15B) andprocessing it together with active material particles and additives 152,e.g., in ball milling 154A, followed by addition of liquid 154B to formelectrode slurry 155, possibly after addition of further electrolyteslurry 120C. The processing of electrolyte particles 125 together withany of electrode particles 110, 110A, 110B may be configured to improvethe contact between them.

Following production of electrode 100, 87 (e.g., to a degree of porositybetween 30-70%), attachment 156 of a solid electrolyte layer 120D mayachieve good contact 156 due to initial electrolyte components 120Cand/or 120D. Alternatively, solid electrolyte layer 120D may be carriedout without prior introduction of electrolyte components 120C and/or120D, possibly utilizing additives in solid electrolyte layer 120Dand/or electrode 100, 87, and possibly pressure 157 to provide goodcontact 156. It is noted that electrolyte 120 may comprise ionicconductive material such as solid electrolyte particles as well as anionic conductive polymer 124 which may be polymerized 124A beforeproduction process 151 or during process 151 at various stages. In anyof the illustrated cases and their combinations, an anode-electrolyteelement 162 (or, generally, an electrode-electrolyte element) is formedand may be used for preparing cells 150. In certain embodiments, seee.g., FIG. 13A, the electrode-electrolyte element may comprise bothanode and cathode attached to the electrolyte, and may be used by anycombination of methods 151A-D.

FIGS. 15D-15G are high-level schematic illustrations of interfacesbetween electrode active material 110 and electrolyte particles 125,according to some embodiments of the invention. It is noted thatelements illustrated in FIGS. 13A, 13B, 14A, 14B, 14D-14H and 15D-15Gmay be combined to provide additional embodiments which are notillustrated explicitly. It is further noted that while the illustratedembodiments refer to anodes 100, equivalent configurations may beprepared for cathodes 87.

FIG. 15D illustrates schematically porous anode 100 (or cathode 87)having schematically-illustrated pores 111. FIG. 15E illustratesschematically the filling of pores 111 by electrolyte 120 withelectrolyte particles 125 (clearly the relative sizes of the particlesare non-limiting and are for illustration purposes alone), for exampleby liquid electrolyte 120 and/or electrolyte 120 in solution (see 120Ain FIG. 15A) being dried or evaporated to achieve goodelectrolyte-electrode contact 156. FIG. 15F illustrates schematicallyelectrode-electrolyte contact which may be achieve by (i) using liquidelectrolyte 120 and/or electrolyte 120 in solution (120A in FIG. 15A) tofill pores 111 as well as form electrolyte 120 and/or (ii) usingelectrolyte material as additive (120B in FIG. 15B) and/or electrolytematerial in the slurry (120C in FIG. 15B) to prepare anode 100 withembedded electrolyte material, and then attach solid electrolyte layerthereto (120D in FIG. 15B) to yield good attachment 156. FIG. 15Gillustrates schematically application of pressure 160A on electrolyte120 (in any of its disclosed configurations, e.g., as illustrated inFIG. 15F) to further improve contact 156 between electrode 100 andelectrolyte 120.

FIG. 16 is a high-level flowchart illustrating a method 400, accordingto some embodiments of the invention. The method stages may be carriedout with respect to composite electrolyte 120 and/or lithium ion cell(s)150 described above, which may optionally be configured to implementmethod 400. Method 400 may comprise stages for producing, preparingand/or using composite electrolyte 120 and/or lithium ion cell(s) 150,such as any of the following stages, irrespective of their order. Invarious embodiments, method 400, processes 151 (see FIGS. 3A-3C) and/orstages thereof may be implemented as part of any of methods 200 and/or300 disclosed above.

Method 400 comprises coating solid electrolyte particles by flexibleionic conductive material (stage 410) and using the coated particles ascomposite electrolyte in a lithium ion cell (stage 420). Method 400 mayfurther comprise configuring the flexible ionic conductive material inthe lithium ion cell to increase a contact area between the solidelectrolyte particles and electrode active material particles (stage430). Alternatively or complementarily, method 400 may further compriseconfiguring the flexible ionic conductive material in the lithium ioncell to provide an ionic conduction path through the flexible ionicconductive material (stage 440).

Method 400 may further comprise bonding the solid electrolyte particlesto electrode active material in the lithium ion cell by bondingmolecules in the flexible ionic conductive material (stage 450) and/orbonding ionic liquid ions in the lithium ion cell to the solidelectrolyte particles by bonding molecules in the flexible ionicconductive material (stage 460). The ionic liquid may be used asadditional electrolyte or as an additive thereto, with the cells furthercomprising a separator as described above.

Method 400 may further comprise attaching composite electrolyte layer(s)to the anode and to the cathode (stage 470), possibly applying stages ofproduction process 151 illustrated schematically in FIGS. 15A-15C.

Advantageously, using solid electrolyte particles coated by flexibleionic conductive material as a solid-state electrolyte improves theenergy density and safety with respect to liquid electrolyte (e.g.,concerning safety, solid state electrolyte dismisses with volatilesubstances which may present a risk upon dendrite formation) whilesolving prior art problems of low ionic conductivity, especially at lowtemperatures, which leads to low C rate capability. The disclosedelectrolytes may be configured to enable batteries which operate at highC rate and/or low temperatures, by providing high ionic conductivity.

Electrolytes, lithium ion cells and corresponding methods are provided,for extending the cycle life of fast charging lithium ion batteries. Theelectrolytes may comprise organic solvent(s) with at least one lithiumsalt which provides lithium ions for the operation of the lithium ioncell. The electrolytes are based on fluoroethylene carbonate (FEC)and/or vinylene carbonate (VC) as the cyclic carbonate component, andpossibly on ethyl acetate (EA), propyl acetate and/or propionates;and/or ethyl methyl carbonate (EMC) as the linear component. Proposedelectrolytes extend the cycle life by factors of two or more, asindicated by several complementary measurements.

In certain embodiments, electrolyte 105 may have at least one linearcomponent and at least one cyclic carbonate component, of which thecyclic carbonate component(s) may comprise at least 80% of FEC and/orVC. In certain embodiments, electrolyte 105 may comprise at least 10%vol FEC and/or VC, and/or 20-50% vol FEC and/or VC as the cycliccarbonate component(s).

In certain embodiments, the at least one linear component of electrolyte105 may comprise at least 30% of ethyl acetate (EA) and/or propylacetate and/or propionates. In certain embodiments, a volume ratiobetween the at least one cyclic carbonate component and the at least onelinear component may be between 2:8 and 1:1. In certain embodiments,electrolyte 105 may comprise at least one lithium electrolyte salt, suchas 0.9-1.3M LiPF₆ or any other lithium salt(s). Examples fornon-limiting specific compositions of electrolytes 105 are providedbelow.

In certain embodiments, the at least one linear component of electrolyte105 may comprise at least 20% vol or at least 30% vol of any of ethylacetate (EA), propyl acetate and propionates; and/or any of: ethylacetate (EA), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC),diethyl carbonate (DEC), modified linear carbonates and fluorinatedlinear carbonates.

In certain embodiments, electrolyte 105 may comprise 20-50% vol FECand/or VC. In certain embodiments, electrolyte 105 may comprise 20-60%vol EA and/or propyl acetate and propionates. In certain embodiments,electrolyte 105 may comprise 50-80% vol EMC. In certain embodiments,electrolyte 105 may comprise 20-50% vol FEC and/or VC and 80-50% vol EAand/or EMC. In certain embodiments, electrolyte 105 may comprise between20-40% vol FEC, between 20-40% vol EA and between 20-60% vol EMC.

While FEC and VC are known in prior art to be used as electrolyteadditives to EC:DMC (ethylene carbonate: dimethyl carbonate, e.g., inratios 1:1 or 3:7, possibly including also DEC or EMC at 1:1:1 ratioswith EC and DMC) electrolytes, typically at weight % of a few %, theinventors discovered that FEC-based electrolytes 105 and/or VC-basedelectrolytes 105—having FEC and/or VC as the main cyclic carbonatecomponent—improve performance of lithium ion cells 150, particularlylithium ion cells 150 configured to enable fast charging rates (seedetails below). Lithium ion cells 150 may comprise metalloids such as,but not limited to, Si, Ge and/or Sn as at least part of their anodematerial and/or possibly graphene and/or lithium titanate (LTO) or evengraphite, as at least part of their anode material.

In certain embodiments, proposed electrolytes extend the cycle life byfactors of two or more, as indicated by several complementarymeasurements. In certain embodiments, additional linear carbonates maybe used, such as DEC (diethyl carbonate) and/or modified linearcarbonates such as fluorinated carbonates. Below, a detailedpresentation of electrolyte compositions is provided, in any of thedisclosed embodiments, electrolyte 105 comprises FEC and/or VC as themain cyclic carbonate compound. In certain embodiments the proposedelectrolyte may include other cyclic and linear compounds. In certainembodiments, additional additives may be utilized in the electrolyte 105including but not limiting; SEI formers, HF-scavengers, phosphorous- andsulfur-based components and compounds disclosed above. In certainembodiments, EMC may replace DMC as the linear component of electrolyte105, e.g., to enable using lithium ion cell 150 at temperatures as lowas −30° C. In certain embodiments, electrolyte 105 may consist of 20-30%vol FEC and 80-50% vol EMC and/or 20-30% vol EA and between 50-60% volEMC, a VC additive (e.g., at 2% wt) and at least one lithium electrolytesalt.

The non-aqueous linear organic solvent may include, e.g.,carbonate-based solvent(s), ester-based solvent(s), ether-basedsolvent(s), ketone-based solvent(s), nitrile-based solvent(s), sulfonesolvent(s), and/or aprotic solvent(s). The carbonate-based solvent maycomprise carbonate-based compounds such as any of: dimethyl carbonate(DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropylcarbonate (MPC), ethylpropyl carbonate (EPC), ethylmethyl carbonate(EMC), butylene carbonate (BC), or the like. In certain embodiments,ester-based solvent(s) may comprise any of: methyl acetate, ethylacetate, n-propyl acetate, dimethylacetate, methylpropionate,ethylpropionate, gamma-butyrolactone, decanolide, gamma-valerolactone,mevalonolactone, caprolactone, or the like. In certain embodiments,ether-based solvent(s) may comprise any of: dibutyl ether, tetraglyme,diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, andthe like. In certain embodiments, ketone-based solvent(s) may comprisee.g., cyclohexanone, or the like. In certain embodiments, aproticsolvent(s) may comprise, e.g., nitriles such as R—CN of various typesand/or dinitriles NC—R—CN of various types (e.g., nitriles or dinitrilesin which R is a hydrocarbon group having a C2 to C20 linear, branched,or cyclic structure, and may include a double bond, an aromatic ring, oran ether bond) or the like, amides such as dimethylformamide or thelike, dioxolanes such as 1,3-dioxolane or the like, sulfolanes, or thelike.

In certain embodiments, non-aqueous organic solvent(s) may comprise,e.g., aromatic hydrocarbon-based organic solvent(s) with thecarbonate-based solvent(s). The carbonate-based and the aromatichydrocarbon-based solvents may be mixed together in a volume ratio ofbetween about 1:1 to about 30:1. Examples of the aromatichydrocarbon-based organic solvent may comprise any of: benzene,fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene,1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene,chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene,1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene,iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene,1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene,2,3-difluorotoluene, 2,4-difluorotoluene, 2,5-difluorotoluene,2,3,4-trifluorotoluene, 2,3,5-trifluorotoluene, chlorotoluene,2,3-dichlorotoluene, 2,4-dichlorotoluene, 2,5-dichlorotoluene,2,3,4-trichlorotoluene, 2,3,5-trichlorotoluene, iodotoluene,2,3-diiodotoluene, 2,4-diiodotoluene, 2,5-diiodotoluene,2,3,4-triiodotoluene, 2,3,5-triiodotoluene, xylene, and combinationsthereof. In certain embodiments, non-aqueous solvent(s) may comprisemonosulfonic acid ester compound(s) such as any of: 1,3-propane sultone,1,4-butane sultone, methyl methanesulfonate, methyl ethanesulfonate,methyl trifluoromethanesulfonate and combinations thereof.

One or more lithium salts may be dissolved in the organic solvent(s).The lithium salt(s) may be selected to perform any of the followingfunctions within the battery cells: supply lithium ions in a battery,enable operation of the rechargeable lithium battery, and improvelithium ion transportation between the positive and negative electrodes.Non-limiting examples for lithium electrolyte salt(s) (expressed asLi⁺X⁻ in electrolyte 105) may comprise, as respective anions X⁻, any of:F⁻, Cl⁻, Br⁻, I⁻, NO3⁻, N(CN)₂ ⁻, BF₄ ⁻, ClO₄ ⁻, PF₆ ⁻, (CF₃)₂PF₄ ⁻,(CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, CF₃SO₃ ⁻, CF₃CF₂SO₃ ⁻,(CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, CF₃CF₂ (CF₃)₂CO⁻, and combinations thereof. Thelithium salt(s) may be included in electrolyte 105 in a concentration ofbetween about 0.1 M to about 2.0 M. The concentration range and valuesmay be selected to optimize the performance and the lithium ion mobilitywith respect to electrolyte conductivity and viscosity.

Various additive(s) and their combinations may be added to electrolyte105, such as solid electrolyte interphase (SEI) forming additives,compounds that promote high temperature stability and HF scavengerswhich prevent battery capacity deterioration, as disclosed below.

In certain embodiments, SEI forming additives comprise materials thatcan be reductively decomposed on surfaces of negative electrodes priorto other solvent components, to form protective films (SEI films) thatsuppress excessive decomposition of the electrolytic solutions, enhancecharge/discharge efficiency and/or improve the cycle characteristics andthe safety of non-aqueous electrolyte batteries. Generally, SEI formerscan include, but not limited to, vinylene carbonate and its derivatives,ethylene carbonate derivatives having non-conjugated unsaturated bondsin their side chains, halogen atom-substituted cyclic carbonates andsalts of chelated orthoborates and chelated orthophosphates. Specific,non-limiting, examples of SEI forming additives which may be used inelectrolyte 105 comprise any of: VC, vinylethylene carbonate (VEC),methylene ethylene carbonate (or 4-vinyl-1,3-dioxolan-2-one) (MEC),chloroethylene carbonate (CEC), 4,5-divinyl-1,3-dioxolan-2-one,4-methyl-5-vinyl-1,3-dioxolan-2-one, 4-ethyl-5-vinyl-1,3-dioxolan-2-one,4-propyl-5-vinyl-1,3-dioxolan-2-one, 4-butyl-5-vinyl-1,3-dioxolan-2-one,4-pentyl-5-vinyl-1,3-dioxolan-2-one, 4-hexyl-5-vinyl-1,3-dioxolan-2-one,4-phenyl-5-vinyl-1,3-dioxolan-2-one, 4,4-difluoro-1,3-dioxolan-2-one and4,5-difluoro-1,3-dioxolan-2-one, lithium bis(oxalate)borate (LiBOB),lithium bis(malonato)borate (LiBMB), lithium bis(difluoromalonato)borate(LiBDFMB), lithium (malonato oxalato)borate (LiMOB), lithium(difluoromalonato oxalato)borate (LiDFMOB), lithiumtris(oxalato)phosphate (LiTOP), and lithiumtris(difluoromalonato)phosphate (LiTDFMP). Particularly useful SEIformers may be selected from FEC, VC, monofluoroethylene carbonate, MEC,VEC, LiBOB and mixtures thereof. The amount of SEI former may rangebetween 0.1% to 8% of the total electrolyte weight. In certainembodiments, the amount of SEI former may range between 1% to 5% of thetotal electrolyte weight.

In certain embodiments, high temperature stabilizer additives may beselected to promote high temperature stability, e.g., by enhancingcapacity retention at high temperatures (e.g., above 50° C.) andpreventing swelling and gas generation, e.g., by preventingdecomposition of the electrolyte at the cathode. High temperaturestabilizer additives may be particularly effective in cells operating athigh voltages and/or in cells operating at high charging rates, and theymay be selected to enhance charge-discharge characteristics of thebatteries and effectively reduce the swelling of batteries at elevatedtemperatures. High temperature stabilizer additives may be selected tohelp to create a protective layer on the surface of the cathode whichfurther decreases the amount of solvent oxidation and decomposition atthe cathode.

Electrolyte 105 may comprise compounds that promote high temperaturestability such as any of: sulfur-containing linear and heterocyclic,unsaturated and saturated compounds; phosphorus containing linear andheterocyclic, unsaturated and saturated compounds; as well as HFscavenging compounds. Sulfur containing compounds may comprise linearand cyclic compounds such as sulfites, sulfates, sulfoxides, sulfonates,thiophenes, thiazoles, thietanes, thietes, thiolanes, thiazolidines,thiazines, sultones, and sulfones. These sulfur-containing compounds caninclude various degrees of fluorine substitution up to and including thefully perfluorinated compounds. Certain embodiments may comprise any ofthe following non-limiting examples of sulfur-containing linear andcyclic compounds: ethylene sulfite, ethylene sulfate, thiophene,benzothiophene, benzo[c]thiophene, thiazole, dithiazole, isothiazole,thietane, thiete, dithietane, dithiete, thiolane, dithiolane,thiazolidine, isothiazolidine, thiadiazole, thiane, thiopyran,thiomorpholine, thiazine, dithiane, dithiine; thiepane; thiepine;thiazepine; prop-1-ene-1,3-sultone; propane-1,3-sultone;butane-1,4-sultone; 3-hydroxy-1-phenylpropanesulfonic acid 1,3-sultone;4-hydroxy-1-phenylbutanesulfonic acid 1,4-sultone;4-hydroxy-1-methylbutanesulfonic acid 1,4 sultone;3-hydroxy-3-methylpropanesulfonic acid 1,4-sultone;4-hydroxy-4-methylbutanesulfonic acid 1,4-sultone; a sulfone having theformula R—S(═O)₂—R′ where R and R′ are independently selected from thegroup consisting of substituted or unsubstituted, saturated orunsaturated C1 to C20 alkyl or aralkyl groups; and combinations of twoor more thereof. In certain embodiments, sulfur-containing compounds maybe selected from propane-1,3-sultone, butane-1,4-sultone andprop-1-ene-1,3-sultone, each provided in an amount of 0.1 to 5.0% byweight of the electrolyte solution. Electrolyte 105 may comprisephosphorus-containing compounds such as linear and cyclic, phosphatesand phosphonates. Electrolyte 105 may comprise any of the followingphosphorus-containing compounds: alkyl phosphates, such as trimethylphosphate, triethyl phosphate, tri-isopropyl phosphate, propyl dimethylphosphate, dipropyl methyl phosphate, and tripropyl phosphate; aromaticphosphates, such as triphenyl phosphate; alkyl phosphonates includetrimethylphosphonate, and propyl dimethylphosphonate; and aromaticphosphonates, such as phenyl dimethylphosphonate; as well ascombinations thereof. Electrolyte 105 may comprise phosphorus-containingcompounds at an amount which is between 0.1% and 5% of the totalelectrolyte weight.

Electrolyte 105 may comprise HF scavenger compounds selected to preventbattery capacity deterioration and improve output characteristics athigh temperatures. HF scavenger compounds may comprise acetamides,anhydrides, pyridines, tris(trialkylsilyl)phosphates,tris(trialkylsilyl)phosphites, tris(trialkylsilyl)borates. Electrolyte105 may comprise any of: acetamides such as, N,N-dimethyl acetamide, and2,2,2-trifluoroacetamide; anhydrides such as phthalic anhydride succinicanhydride, and glutaric anhydride; pyridines such as antipyridine andpyridine; tris(trialkylsilyl)phosphates such astris(trimethylsilyl)phosphate and tris(triethylsilyl)phosphate;tris(trialkylsilyl)phosphites tris(trimethylsilyl)phosphite,tris(triethylsilyl)phosphite, tris(tripropylsilyl)phosphit;tris(trialkylsilyl)borates such as, tris(trimethylsilyl)borate,tris(triethylsilyl)borate, and tris(tripropylsilyl)borate; alone or as amixture of two or more thereof. Electrolyte 105 may comprise HFscavenger compounds at an amount which is between 0.1% to 5% of thetotal electrolyte weight.

Ionic liquid additive(s) may be added to electrolyte 105 as disclosede.g., in U.S. patent application Ser. Nos. 15/447,784 and 15/447,889,both filed on Mar. 2, 2017, which are incorporated herein by referencein their entirety; for example, ionic liquids based on sulfonylimidesand piperidinium derivatives having relatively low melting temperaturesin any of the ranges 10-20° C., 0-10° C., or possibly even <0° C., <−20°C., and/or <−40° C.

The inventors have found out that replacing the prior art cycliccarbonate component EC with FEC and/or VC improves the cycle life of thecells, particularly in fast charging applications—as illustrated e.g.,in FIGS. 20A-20J. In certain embodiments, cell lifetime (e.g., in termsof capacity retention, coulombic efficiency etc.) was doubled usingdisclosed electrolytes 105, providing a significant improvement withrespect to a bottleneck in the development of metalloid-based (e.g.,comprising Si, Ge and/or Sn anode material), LTO, graphene and/or fastcharging cells 150. Disclosed electrolytes may be beneficial forgraphite-based anodes as well, possibly with additions of metalloidsand/or possibly metalloid-based anodes with additions of graphite.

Preparation

Electrolyte 105 may be prepared from a baseline electrolyte, prepared bydissolving LiPF₆ into FEC (possibly with additional cyclic compounds)and linear compounds so that the LiPF₆ concentration is above 1 mol/L.The amount of FEC is above 10% vol, preferably between 20-50% vol. VCwas added into the baseline electrolyte in the amount of 0.5-2.5%.

Cathode(s) 87 in lithium ion battery 150 comprises cathode activematerial that can reversibly intercalate and de-intercalate lithiumions. As a non-limiting example, the cathode active material may be acomposite metal oxide of lithium and at least one selected from cobalt,manganese and nickel. The solid solubility of metals may be variouslyused in the composite metal oxide. In addition to these metals, any oneselected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, Sn,V, Ge, Ga, B, As, Zr, Mn, Cr, Fe, Sr, V and rare earth elements may befurther included. In certain embodiments, cathode(s) 87 may comprisematerials based on layered, spinel and/or olivine frameworks, andcomprise various compositions, such as LCO formulations (based onLiCoO₂), NMC formulations (based on lithium nickel-manganese-cobalt),NCA formulations (based on lithium nickel cobalt aluminum oxides), LMOformulations (based on LiMn₂O₄), LMN formulations (based on lithiummanganese-nickel oxides) LFP formulations (based on LiFePO₄), lithiumrich cathodes, and/or combinations thereof. The cathode may be made bypreparing an electrode slurry composition by dispersing the electrodeactive material, a binder, a conductive material and a thickener, ifdesired, in a solvent and coating the slurry composition on an electrodecollector. As non-limiting examples, aluminum or aluminum alloy may beused as a cathode collector. The cathode collector may be formed as afoil or mesh. Separator(s) 86 may comprise various materials, such aspolyethylene (PE), polypropylene (PP) or other appropriate materials. Asnon-limiting examples, a polymer membrane such as a polyolefin,polypropylene, or polyethylene membrane, a multi-membrane thereof, amicro-porous film, or a woven or non-woven fabric may be used as theseparator. Possible compositions of anode(s) 100 are disclosed below indetail

FIG. 17 is a high-level flowchart illustrating a method 500, accordingto some embodiments of the invention. The method stages may be carriedout with respect to lithium ion cell 150 and/or electrolyte 105described above. Method 500 may comprise stages for producing, preparingand/or using lithium ion cell 150 and/or electrolyte 105, such as any ofthe following stages, irrespective of their order. In variousembodiments, method 500 and/or stages thereof may be implemented as partof any of methods 200, 300 and/or 400 disclosed herein.

Method 500 may comprise using FEC and/or VC-based electrolytes for cellshaving Si, Ge and/or Sn-based anodes, or possibly graphene and/orLTO-based or even graphite anode material (stage 510), e.g., byreplacing all, or most, cyclic carbonates in the electrolyte (e.g., EC)with FEC and/or VC, possibly reaching, e.g., 30% of FEC and/or VC in theelectrolyte (stage 515). In any of the embodiments, the anodes maycomprise combinations of the anode materials disclosed above, e.g.,metalloids such as Ge or Si with graphite, graphite or graphene withmetalloids such Ge, Si or Sn, or any other combination.

For example, method 500 may comprise preparing the electrolyte from20-50% FEC and/or VC, and 20-60% vol EA and/or 50-80% vol DMC and/or EMC(stage 520) and possibly adding additives (e.g., FEC or VC, e.g., at 2%vol, into VC-based and FEC-based electrolytes respectively) and lithiumsalt(s) to the electrolyte (stage 525), e.g., LiPF₆ in concentration0.9-1.3 M.

Method 500 may further comprise using EMC as the linear carbonate and/orEA as linear component to reduce the freezing point of the cell (stage530).

Disclosed electrolytes may be used with improved anodes and cells whichenable fast charging rates with enhanced safety due to much reducedprobability of metallization of lithium on the anode, possiblypreventing dendrite growth and related risks of fire or explosion.Disclosed electrolytes may be used with various anode active materialsand combinations, modifications through nanoparticles and a range ofcoatings which implement the improved anodes as illustratedschematically in FIG. 1B.

Examples

Disclosed electrolytes 105 were shown to increase cycle life in fastcharging cells 150 having metalloid-based (e.g., anode materialcomprising Si, Ge and/or Sn) anode(s).

FIGS. 18A-18D demonstrate the increased cell life for using electrolyte105, according to some embodiments of the invention, with respect tousing prior art electrolytes, in half cell experimental setting foranodes 100 having Ge anode material. FIGS. 18A and 18B present,respectively, the coulombic efficiency (CE) and the capacity retentionof half-cells having Ge-based anode 100 (and lithium electrode ascathode 87) with prior art electrolyte (1M LiPF₆ in EC:DMC (1:1) with 2wt % VC) with respect to electrolyte 105 (1M LiPF₆ in FEC:DMC (1:1) with2 wt % VC) having FEC replacing EC as the cyclic carbonate. As clearlyshown in FIGS. 18A and 18B, both the coulombic efficiency and thecapacity retention are much higher when using electrolyte 105 withGe-based anode 100. FIGS. 18C and 18D present, respectively, thecoulombic efficiency (CE) and the capacity retention of half-cellshaving Si:Sn-based anode 100 (and lithium electrode as cathode 87) withprior art electrolyte (1M LiPF₆ in EC:DMC (1:1) with 2 wt % VC) withrespect to electrolyte 105 (1M LiPF₆ in FEC:DMC (1:1) with 2 wt % VC)having FEC replacing EC as the cyclic carbonate. As clearly shown inFIGS. 18C and 18D, both the coulombic efficiency and the capacityretention are much higher when using electrolyte 105 with Si:Sn-basedanode 100 as well.

FIGS. 19A-19C demonstrate the increased performance for usingelectrolytes according to some embodiments of the invention, withrespect to using prior art electrolytes, at high C rate in full cellexperimental setting. The full cells, having Ge anode 100, a NCA cathode87 and electrolyte 105 (1M LiPF₆ in FEC:DMC (1:1) with 2 wt % VC) wereoperated at 10C charging rate (and 0.5 C discharging rate) and comparedto similar cells with prior art electrolyte (1M LiPF₆ in EC:DMC (1:1)with 10% wt FEC). FIG. 19A illustrates the increase in the number ofcycles by ca. 50% (from ca. 250 to ca. 375) achieved using electrolyte105 (mean, standard deviation and quantiles shown for three runs withthe disclosed electrolyte and two runs with prior art electrolyte). FIG.19B illustrates the much smaller slope of capacity degradation (ca.−0.02 compared with ca. −0.15) achieved using electrolyte 105 (mean,standard deviation and quantiles shown for three runs with the disclosedelectrolyte and two runs with prior art electrolyte). FIG. 19Cillustrates the higher ratio of capacity at 10C charging rate withrespect to IC charging rate (ca. 100 compared with ca. 75, respectively)achieved using electrolyte 105 (mean, standard deviation and quantilesshown for seventeen runs with the disclosed electrolyte and three runswith prior art electrolyte). The disclosed experimental data exemplifiesthe extraordinary improvement achieved by using disclosed electrolytes105 having FEC (at 20-50% vol) as the cyclic carbonate thereof.

FIGS. 20A-20J provide a range of examples for disclosed electrolytecompositions 105 which outperform prior art electrolytes, according tosome embodiments of the invention. All graphs show the capacityretention of cells having either electrolyte, with disclosedelectrolytes 105 providing in most cases two to three-fold extensions ofthe cell lifetime. Disclosed electrolytes 105 in each of FIGS. 20A-20Jare provided below. In FIG. 20A the anode material is tin-silicon-based,the examples are carried out in a full cell configuration, and the priorart electrolyte is 1M LiPF6 EC:DMC (1:1) 10 wt % FEC. In FIGS. 20B-20Ithe anode material is germanium-based, the examples are carried out infull cells configurations, and the prior art electrolyte is 1M LiPF6EC:DMC (1:1) 10 wt % FEC, and in FIG. 20J the anode material isLTO-based, the example is carried out in a half cell configuration, andthe prior art electrolyte is 1M LiPF₆ EC:DMC (1:1) 2 wt % VC. In allexamples, the cells (and half-cell) are cycled at highcharging/discharging rates of 10C.

Examples for tested electrolytes 105 comprise the following non-limitingexamples: 1.3M LiPF₆ FEC:DMC (1:1) 2 wt % VC (FIG. 20C); 1M LiPF₆FEC:DMC (3:7) 2 wt % VC; 1M LiPF₆ FEC:DMC (3:7) 2 wt % VC 10 wt % EC; 1MLiPF₆ FEC:DEC (1:1) 2 wt % VC; 1M LiPF₆ FEC:DEC (3:7) 2 wt % VC (FIGS.20A and 20J); 1M LiPF₆ FEC:EMC 3:7 2 wt % VC; 1M LiPF₆ FEC:PC:EMC(2:3:5) 2 wt % VC; 1M LiPF₆ FEC:DMC (1:1) 2% VC 10 wt % TMP (trimethylphosphate) 0.05M LIFOB; 1M LiPF₆ FEC:DMC (1:1) 2% VC 10 wt % TMP 0.5 wt% TMSP (tris(trimethylsilyl)phosphite) (FIG. 20D); 1M LiPF₆ FEC:DMC(1:1) 2 wt % VC 10 wt % TMP 0.05M LIFOB 0.5 wt % TMSP; 1M LiPF₆ FEC:DMC(1:1) 2 wt % VC 10 wt % TMP 0.05M LIBOB; 1M LiPF₆ FEC:DMC (1:1) 2 wt %VC 10 wt % TMP 1 wt % DPDMS (diphenyldimethoxysilane); 1M LiPF₆ FEC:EMC(3:7) 2 wt % VC 10 wt % TMP (FIG. 20B); 1M LiPF₆ FEC:EMC (3:7) 2 wt % VC10 wt % MFE; 1M LiPF₆ FEC:DMC (3:7) 2 wt % VC 10 wt % TMP; 1M LiPF₆FEC:DMC (1:1) 2 wt % VC 10 wt % TMP; 1M LiPF₆ FEC:EMC (2.5:7.5) 1.5 wt %VC (FIG. 20E); and 1M LiPF₆ FEC:EMC:DMC (2.5:6.5:1) 0.5 wt % VC (FIG.20F); 1M LiPF₆ VC:EA:EMC (3:3.5:3.5) (FIG. 20I); 1M LiPF₆ VC:EMC (3:7)(FIG. 20G); 1M LiPF₆ FEC:EMC (3:7) (FIG. 20H). These compositions weretested and found at least as good as, or better than prior artelectrolyte composition 1M LiPF₆ EC:DMC 1:1 10 wt % FEC with respect tocapacity retention after fast charging (at 10C) and cycle lifetime underhigh C cycling.

In the above description, an embodiment is an example or implementationof the invention. The various appearances of “one embodiment”, “anembodiment”, “certain embodiments” or “some embodiments” do notnecessarily all refer to the same embodiments. Although various featuresof the invention may be described in the context of a single embodiment,the features may also be provided separately or in any suitablecombination. Conversely, although the invention may be described hereinin the context of separate embodiments for clarity, the invention mayalso be implemented in a single embodiment. Certain embodiments of theinvention may include features from different embodiments disclosedabove, and certain embodiments may incorporate elements from otherembodiments disclosed above. The disclosure of elements of the inventionin the context of a specific embodiment is not to be taken as limitingtheir use in the specific embodiment alone. Furthermore, it is to beunderstood that the invention can be carried out or practiced in variousways and that the invention can be implemented in certain embodimentsother than the ones outlined in the description above.

The invention is not limited to those diagrams or to the correspondingdescriptions. For example, flow need not move through each illustratedbox or state, or in exactly the same order as illustrated and described.Meanings of technical and scientific terms used herein are to becommonly understood as by one of ordinary skill in the art to which theinvention belongs, unless otherwise defined. While the invention hasbeen described with respect to a limited number of embodiments, theseshould not be construed as limitations on the scope of the invention,but rather as exemplifications of some of the preferred embodiments.Other possible variations, modifications, and applications are alsowithin the scope of the invention. Accordingly, the scope of theinvention should not be limited by what has thus far been described, butby the appended claims and their legal equivalents.

The invention claimed is:
 1. A lithium ion cell comprising: at least oneanode comprising anode active material which consists of Si, Ge and/orSn, at least one cathode, and an electrolyte consisting of at least onesolvent, at least one linear carbonate component, at least one cycliccarbonate component, at least one lithium salt and optional additives upto 2%, wherein the at least one cyclic carbonate component comprises atleast 20% vol of vinylene carbonate (VC), and wherein the lithium ioncell is configured to operate at a fast charging rate of at least 10C,and wherein the electrolyte has a 3:7 ratio between the VC and the atleast one linear carbonate component.
 2. The lithium ion cell of claim1, wherein the at least one linear carbonate component comprises any of:ethyl acetate (EA), dimethyl carbonate (DMC), ethyl methyl carbonate(EMC), diethyl carbonate (DEC), modified linear carbonates andfluorinated linear carbonates.
 3. The lithium ion cell of claim 1,wherein the at least one linear carbonate component comprises at least30% of at least one of: ethyl acetate (EA), propyl acetate andpropionates.
 4. The lithium ion cell of claim 1, wherein the electrolytecomprises, as the at least one linear carbonate component, at least 20%vol EA, propyl acetate and/or propionates, and at least 50% vol EMC. 5.The lithium ion cell of claim 1, wherein the at least one solventcomprises any of: esters-based solvents, sulfones-based solvents,nitriles-based solvents, ethers-based solvents, alcohol-based solvents,hydrocarbons, aprotic-based solvents, a SEI forming additive, a HFscavenger additive, a phosphorous-containing compounds and mixturesthereof.
 6. An energy storage device comprising the lithium ion cell ofclaim
 1. 7. A method comprising using an electrolyte in a lithium ioncell which comprises at least one anode with anode active materialconsisting of Si, Ge and/or Sn the lithium ion cell configured tooperate at a fast charging rate of at least 10C, wherein all or mostcyclic carbonates are VC, wherein the VC makes up 30% of theelectrolyte, and wherein all or most linear carbonate components are EAand/or EMC.
 8. A lithium ion cell comprising: at least one anodecomprising anode active material which consists of Si, Ge and/or Sn, atleast one cathode, and an electrolyte consisting of at least one linearcarbonate component, at least one cyclic carbonate component, at leastone lithium salt and optional additives up to 2%, wherein the at leastone cyclic carbonate component comprises at least 20% vol of vinylenecarbonate (VC) and/or fluoroethylene carbonate (FEC), and wherein thelithium ion cell is configured to operate at a fast charging rate of atleast 10C, and wherein the electrolyte is selected from 1-1.3M LiPF₆ inFEC:DMC (1:1) and 2 wt % VC; 1M LiPF₆ in FEC:DMC (3:7) and 2 wt % VC; 1MLiPF₆ in FEC:DMC (3:7), 2 wt % VC and 10 wt % EC; 1M LiPF₆ in FEC:DEC(3:7) and 2 wt % VC; 1M LiPF₆ in FEC:EMC (3:7) and 2 wt % VC; 1M LiPF₆in FEC:PC:EMC (2:3:5) and 2 wt % VC; 1M LiPF₆ in FEC:DMC (1:1), 2% VC,10 wt % TMP (trimethyl phosphate) and 0.05M LIFOB (lithiumdifluoro(oxalato)borate); 1M LiPF₆ in FEC:DMC (1:1), 2 wt % VC, 10 wt %TMP and 0.5 wt % TMSP (tris(trimethylsilyl)phosphite); 1M LiPF₆ inFEC:DMC (1:1), 2 wt % VC, 10 wt % TMP, 0.05M LIFOB and 0.5 wt % TMSP; 1MLiPF₆ in FEC:DMC (1:1), 2 wt % VC, 10 wt % TMP, and 0.05M LIBOB (lithiumbis(oxalato)borate); 1M LiPF₆ in FEC:DMC (1:1), 2 wt % VC 10 wt % TMP 1wt % DPDMS (diphenyldimethoxysilane); 1M LiPF₆ in FEC:EMC (3:7), 2 wt %VC and 10 wt % TMP; 1M LiPF₆ in FEC:EMC (3:7), 2 wt % VC and 10 wt % MFE(methylperfluorobutylether); 1M LiPF₆ in FEC:DMC (3:7), 2 wt % VC and 10wt % TMP; 1M LiPF₆ in FEC:DMC (1:1), 2 wt % VC and 10 wt % TMP; 1M LiPF₆in FEC:EMC (2.5:7.5) and 1.5 wt % VC; 1M LiPF₆ in FEC:EMC:DMC(2.5:6.5:1) and 0.5 wt % VC; 1M LiPF₆ in VC:EA (ethylene acetate):EMC(3:3.5:3.5); 1M LiPF₆ in VC:EMC (3:7); and 1M LiPF₆ FEC:EMC (3:7). 9.The lithium ion cell of claim 8, wherein the electrolyte is selectedfrom 1.3M LiPF6 in FEC:DMC (1:1) and 2 wt % VC; 1M LiPF6 in FEC:DEC(3:7) and 2 wt % VC; 1M LiPF6 in FEC:DMC (1:1), 2 wt % VC, 10 wt % TMPand 0.5 wt % TMSP (tris(trimethylsilyl)phosphite); 1M LiPF6 in FEC:DMC(1:1), 2 wt % VC and 10 wt % TMP; 1M LiPF6 in FEC:EMC (2.5:7.5) and 1.5wt % VC; 1M LiPF6 in FEC:EMC:DMC (2.5:6.5:1) and 0.5 wt % VC; 1M LiPF6in VC:EA (ethylene acetate):EMC (3:3.5:3.5); 1M LiPF6 in VC:EMC (3:7);and 1M LiPF6 FEC:EMC (3:7).
 10. A lithium ion cell comprising: at leastone anode comprising anode active material which consists of Si, Geand/or Sn, at least one cathode, and an electrolyte consisting of atleast one linear carbonate component, at least one cyclic carbonatecomponent, at least one lithium salt and optional additives up to 2%,wherein the at least one cyclic carbonate component comprises at least20% vol of vinylene carbonate (VC), and wherein the lithium ion cell isconfigured to operate at a fast charging rate of at least 10C, andwherein the electrolyte consists of 0.9-1.3M LiPF₆ in 20-40% vol VC andone of: 20-40% vol EA, 20-40% vol EA, 40-60% vol EMC or 80-60% vol EMC,wherein the VC and EA and/or EMC add up to 100%.